CN103965564B - Plasticized polyvinyl chloride material and preparation method thereof - Google Patents

Abstract

Translated fromChinese

本发明涉及一种新型无毒增塑聚氯乙烯材料，其包含A)100重量份的PVC树脂；B)20‑80重量份的一种或多种选自下组的主增塑剂：环己烷‑1,2‑二甲酸二异辛酯、环己烷‑1,2‑二甲酸二异壬酯、柠檬酸三丁酯和乙酰柠檬酸三丁酯；以及C)5‑20重量份作为辅增塑剂的乙烯‑醋酸乙烯酯‑羰基共聚物。该材料无毒环保，无增塑剂的迁出现象，透明性佳，加工温度适宜，综合机械性能优异，可以广泛用于食品包装和医疗器械等领域。本发明还涉及所述增塑聚氯乙烯材料的制备方法及在食品包装和医疗器械中的应用。The present invention relates to a novel non-toxic plasticized polyvinyl chloride material, which comprises A) 100 parts by weight of PVC resin; B) 20-80 parts by weight of one or more main plasticizers selected from the following group: ring Diisooctyl hexane‑1,2‑dicarboxylate, diisononyl cyclohexane‑1,2‑dicarboxylate, tributyl citrate, and acetyl tributyl citrate; and C) 5‑20 parts by weight Ethylene-vinyl acetate-carbonyl copolymers as secondary plasticizers. The material is non-toxic and environmentally friendly, has no migration of plasticizers, has good transparency, suitable processing temperature, and excellent comprehensive mechanical properties, and can be widely used in food packaging and medical equipment and other fields. The invention also relates to the preparation method of the plasticized polyvinyl chloride material and its application in food packaging and medical equipment.

Description

Translated fromChinese

增塑聚氯乙烯材料及其制备Plasticized polyvinyl chloride material and its preparation

技术领域technical field

本发明涉及一种增塑聚氯乙烯材料，该材料无毒，可在食品包装、医疗器械等领域广泛应用，尤其用于食品包装袋和膜、输液管、输液袋、输血管、输血袋。本发明还涉及所述材料的制备方法和应用。The invention relates to a plasticized polyvinyl chloride material, which is non-toxic and can be widely used in food packaging, medical equipment and other fields, especially for food packaging bags and films, transfusion tubes, transfusion bags, blood transfusion vessels and blood transfusion bags. The invention also relates to the preparation method and application of said material.

背景技术Background technique

聚氯乙烯(下文有时简称PVC)类材料在医疗设备中有着广泛的应用，主要原因在于聚氯乙烯类材料本身具有良好的物理性质。具体而言，这些物理性质包括：PVC材料加工的方便性以及这类材料与静脉注射液和血液之间良好的相容性。纯PVC材料的硬度、柔性等固有性质都可以通过增塑剂的添加而得到改进。增塑剂的作用在于：增加聚合物的柔性、伸长率或处理(加工)的方便性。Polyvinyl chloride (hereinafter sometimes referred to as PVC) materials are widely used in medical equipment, mainly because the polyvinyl chloride materials themselves have good physical properties. Specifically, these physical properties include: the ease of processing of PVC materials and the good compatibility of such materials with intravenous fluids and blood. The inherent properties such as hardness and flexibility of pure PVC materials can be improved by adding plasticizers. The role of the plasticizer is to increase the flexibility, elongation or ease of handling (processing) of the polymer.

在医疗护理方面(例如：静脉注射血液袋、静脉注射管、人工肾结缔组织导管、鼓泡型氧合器、灌肠剂引流袋和导尿引流袋)通常所使用的PVC类产品中都含有邻苯二甲酸二己酯(下文有时简称DEHP)增塑剂。DEHP作为最经济有效并且广泛使用的增塑剂之一，它的作用在于使PVC具有柔软性和易弯曲性。PVC products commonly used in medical care (such as: IV blood bags, IV tubing, artificial kidney connective tissue catheters, bubble oxygenators, enema drainage bags, and catheter drainage bags) contain adjacent Dihexyl phthalate (hereinafter sometimes referred to as DEHP) plasticizer. As one of the most cost-effective and widely used plasticizers, DEHP is used to make PVC soft and flexible.

但是，近年来发现，DEHP等邻苯二甲酸酯类增塑剂在使用过程中会发生浸出现象，导致病人摄入或吸收一定量的该类增塑剂。然而一旦产生邻苯二甲酸酯增塑剂的吸收，通常认为这些增塑剂会被贮藏在脂肪组织中并且会导致畸形。人们还怀疑DEHP会造成内分泌的紊乱，影响生殖系统的健康，影响孕妇以及新生婴儿的健康，并且与男性生殖道异常具有一定的关系。许多国家，对该类增塑剂纷纷采取了一定措施：欧盟和美国禁止3岁以下儿童玩具和用品使用邻苯二甲酸酯类增塑剂，日本在医疗器械相 关产品中禁止加入该类增塑剂，我国目前也对该类增塑剂采取了一些限制措施。However, in recent years, it has been found that phthalate plasticizers such as DEHP will leach out during use, causing patients to ingest or absorb a certain amount of such plasticizers. However, once absorption of phthalate plasticizers occurs, it is generally believed that these plasticizers are stored in adipose tissue and cause deformities. It is also suspected that DEHP can cause endocrine disorders, affect the health of the reproductive system, affect the health of pregnant women and newborn babies, and have a certain relationship with male reproductive tract abnormalities. Many countries have taken certain measures against such plasticizers: the European Union and the United States prohibit the use of phthalate plasticizers in toys and supplies for children under 3 years old, and Japan prohibits the addition of such plasticizers to medical device-related products At present, my country has also taken some restrictive measures on this type of plasticizer.

因此，目前急需采用新型的无毒环保的增塑剂来对PVC进行改性。专利DE29824628和WO99/32427公开了通过使相应的邻苯二甲酸酯氢化制备的环己烷-1,2-二羧酸酯增塑剂，该类增塑剂有较低的密度和粘度，导致塑料的低温柔软性比相应邻苯二甲酸酯有所改善。也有文献考察其所得塑料的机械性能与用邻苯二甲酸酯得到的相同，并且无毒环保，可以代替邻苯二甲酸酯类增塑剂用于食品包装塑料、医疗器械和儿童玩具中。目前巴斯夫已经开始大量生产Hexamoll DINCH产品(DINCH是环己烷-1,2-二甲酸二异壬酯的简称)，并且在国外的很多食品包装和医疗器械上得到了应用。其他无毒环保型增塑剂还有柠檬酸酯、植物油、高分子增塑剂等等。Therefore, there is an urgent need to use a new type of non-toxic and environmentally friendly plasticizer to modify PVC. Patents DE29824628 and WO99/32427 disclose cyclohexane-1,2-dicarboxylate plasticizers prepared by hydrogenating corresponding phthalates, which have lower density and viscosity, Resulting in improved low-temperature flexibility of plastics compared to corresponding phthalates. There are also literatures to investigate that the mechanical properties of the obtained plastics are the same as those obtained with phthalates, and they are non-toxic and environmentally friendly. They can replace phthalates plasticizers for food packaging plastics, medical devices and children's toys. At present, BASF has begun mass production of Hexamoll DINCH products (DINCH is the abbreviation of diisononyl cyclohexane-1,2-dicarboxylate), and it has been applied in many food packaging and medical devices abroad. Other non-toxic and environmentally friendly plasticizers include citric acid esters, vegetable oils, polymer plasticizers, and the like.

乙烯-醋酸乙烯-羰基(简称EVACO)为一种乙烯三元共聚物，已知可用作PVC的增塑剂。与EVA相比，EVACO由于在分子结构中引入了羰基，使极性提高，促进了与PVC相容。EVACO作为软质PVC改性剂的最大特点是可以阻挡低分子增塑剂的迁移和抽出，但其增塑效率不如低分子酯类增塑剂。Ethylene-vinyl acetate-carbonyl (abbreviated as EVACO) is an ethylene terpolymer known to be useful as a plasticizer for PVC. Compared with EVA, EVACO introduces a carbonyl group in the molecular structure, which increases the polarity and promotes compatibility with PVC. The biggest feature of EVACO as a soft PVC modifier is that it can block the migration and extraction of low-molecular plasticizers, but its plasticizing efficiency is not as good as that of low-molecular ester plasticizers.

发明内容Contents of the invention

鉴于现有技术中的上述状况，本申请的发明人在增塑聚氯乙烯材料领域进行了深入而又广泛的研究，以期发现一种无毒、透明、加工温度适宜、机械性能优异的聚氯乙烯材料。结果发现，将选自环己烷-1,2-二甲酸二异辛酯、环己烷-1,2-二甲酸二异壬酯、柠檬酸三丁酯和乙酰柠檬酸三丁酯这四种增塑剂中的一种或多种作为主增塑剂与乙烯-醋酸乙烯酯-羰基共聚物作为辅增塑剂相结合来增塑PVC，可实现前述目的。乙烯-醋酸乙烯酯-羰基共聚物不仅可以进一步阻止主增塑剂从PVC中迁移和抽出，而且对PVC还表现出增韧作用，使得既可改善增塑作用又可改善韧性和弹性。本发明人正是基于上述发现完成了本发明。In view of the above-mentioned situation in the prior art, the inventors of the present application have carried out in-depth and extensive research in the field of plasticized polyvinyl chloride materials, in order to find a polyvinyl chloride polyvinyl chloride material that is non-toxic, transparent, suitable for processing temperature, and excellent in mechanical properties. vinyl material. As a result, it was found that four compounds selected from diisooctyl cyclohexane-1,2-dicarboxylate, diisononyl cyclohexane-1,2-dicarboxylate, tributyl citrate and acetyl tributyl citrate One or more of the above-mentioned plasticizers can be used as the main plasticizer and ethylene-vinyl acetate-carbonyl copolymer as the auxiliary plasticizer to plasticize PVC to achieve the aforementioned purpose. Ethylene-vinyl acetate-carbonyl copolymer can not only further prevent the migration and extraction of the main plasticizer from PVC, but also exhibit a toughening effect on PVC, so that it can not only improve plasticization, but also improve toughness and elasticity. The present inventors have accomplished the present invention based on the above findings.

因此，本发明的一个目的是提供一种增塑聚氯乙烯材料，该材料无毒，透明性佳，加工温度适宜，综合机械性能优异。Therefore, an object of the present invention is to provide a plasticized polyvinyl chloride material, which is non-toxic, has good transparency, suitable processing temperature and excellent comprehensive mechanical properties.

本发明的另一目的在于提供一种制备本发明增塑聚氯乙烯材料的方法，通过该方法可以简便地制得本发明的材料。Another object of the present invention is to provide a process for preparing the plasticized polyvinyl chloride material of the present invention, by which the material of the present invention can be easily obtained.

本发明的再一目的在于提供本发明增塑聚氯乙烯材料在食品包装和医疗器械中的用途。Another object of the present invention is to provide the use of the plasticized polyvinyl chloride material of the present invention in food packaging and medical devices.

实现本发明上述目的的技术方案可以概括如下：The technical scheme that realizes the above-mentioned purpose of the present invention can be summarized as follows:

1、一种增塑聚氯乙烯材料，其包含如下组分：1. A plasticized polyvinyl chloride material comprising the following components:

A)100重量份的PVC树脂；A) the PVC resin of 100 parts by weight;

B)20-80重量份的一种或多种选自下组的主增塑剂：环己烷-1,2-二甲酸二异辛酯(DEHCH)、环己烷-1,2-二甲酸二异壬酯(DINCH)、柠檬酸三丁酯(TBC)和乙酰柠檬酸三丁酯(ATBC)；以及B) 20-80 parts by weight of one or more main plasticizers selected from the following group: diisooctyl cyclohexane-1,2-dicarboxylate (DEHCH), cyclohexane-1,2-dicarboxylate Diisononyl formate (DINCH), tributyl citrate (TBC), and acetyl tributyl citrate (ATBC); and

C)5-20重量份作为辅增塑剂的乙烯-醋酸乙烯酯-羰基共聚物(EVACO)。C) 5-20 parts by weight of ethylene-vinyl acetate-carbonyl copolymer (EVACO) as a secondary plasticizer.

2、根据第1项所述的增塑聚氯乙烯材料，其中所述PVC树脂包含20-40重量％的平均聚合度为1000-1500、尤其为1000-1300的低聚合度PVC树脂和60-80重量％的平均聚合度为2000-2700、尤其为2000-2500的高聚合度PVC树脂，更优选所述PVC树脂包含20-32重量％的平均聚合度为1000-1500、尤其为1000-1300的低聚合度PVC树脂和68-80重量％的平均聚合度为2000-2700、尤其为2000-2500的高聚合度PVC树脂，基于所述PVC树脂的总重量。2. The plasticized polyvinyl chloride material according to item 1, wherein the PVC resin comprises 20-40% by weight of a low-polymerization degree PVC resin with an average degree of polymerization of 1000-1500, especially 1000-1300, and a 60- 80% by weight of a high degree of polymerization PVC resin with an average degree of polymerization of 2000-2700, especially 2000-2500, more preferably said PVC resin comprises 20-32% by weight of an average degree of polymerization of 1000-1500, especially 1000-1300 PVC resin with a low degree of polymerization and 68-80% by weight of a PVC resin with an average degree of polymerization of 2000-2700, especially 2000-2500, based on the total weight of the PVC resin.

3.根据第1或2项所述的增塑聚氯乙烯材料，其中将环己烷-1,2-二甲酸二异辛酯和/或环己烷-1,2-二甲酸二异壬酯与柠檬酸三丁酯和/或乙酰柠檬酸三丁酯的组合用作主塑化剂。3. The plasticized polyvinyl chloride material according to item 1 or 2, wherein diisooctyl cyclohexane-1,2-dicarboxylate and/or diisononyl cyclohexane-1,2-dicarboxylate Combinations of esters with tributyl citrate and/or acetyl tributyl citrate are used as primary plasticizers.

4.根据第1-3项中任一项所述的增塑聚氯乙烯材料，其中在乙烯-醋酸乙烯酯-羰基共聚物中，乙烯单体单元的含量为58-70重量％，醋酸乙烯酯单元的含量为20-32重量％，和羰基单元的含量为7-15重量％，基于乙烯-醋酸乙烯酯-羰基共聚物的总重量；优选的是，在乙烯-醋酸乙烯酯-羰基共聚物中，乙烯单体单元的含量为60-68重量％，醋酸乙烯酯单元的含量为23-30％，和羰基单元的含量通常为8-12重量％，基于乙烯-醋酸乙烯酯-羰基共聚物的总重量；特别优选使用美国杜邦公司的Elvaloy741型和/或 Elvaloy742型树脂作为乙烯-醋酸乙烯酯-羰基共聚物。4. The plasticized polyvinyl chloride material according to any one of items 1-3, wherein in the ethylene-vinyl acetate-carbonyl copolymer, the content of ethylene monomer units is 58-70% by weight, vinyl acetate The content of ester units is 20-32% by weight, and the content of carbonyl units is 7-15% by weight, based on the total weight of ethylene-vinyl acetate-carbonyl copolymer; preferably, in ethylene-vinyl acetate-carbonyl copolymer In the product, the content of ethylene monomer units is 60-68% by weight, the content of vinyl acetate units is 23-30%, and the content of carbonyl units is usually 8-12% by weight, based on ethylene-vinyl acetate-carbonyl copolymerization The gross weight of thing; Especially preferably use the Elvaloy741 type and/or Elvaloy742 type resin of U.S. DuPont Company as ethylene-vinyl acetate-carbonyl copolymer.

5.根据第1-4项中任一项所述的增塑聚氯乙烯材料，其中该材料基于每100重量份所包含的PVC树脂包含30-70重量份的主增塑剂和5-15份的作为辅增塑剂的乙烯-醋酸乙烯酯-羰基共聚物。5. The plasticized polyvinyl chloride material according to any one of items 1-4, wherein the material comprises 30-70 parts by weight of a primary plasticizer and 5-15 parts by weight based on 100 parts by weight of the PVC resin contained. Parts of ethylene-vinyl acetate-carbonyl copolymer as a secondary plasticizer.

6.根据第1-5项中任一项所述的增塑聚氯乙烯材料，其中该材料基于每100重量份所包含的PVC树脂，还包含如下组分：6. The plasticized polyvinyl chloride material according to any one of items 1-5, wherein the material further comprises the following components based on 100 parts by weight of the PVC resin contained:

D)1-10重量份的环氧大豆油；D) the epoxidized soybean oil of 1-10 weight part;

E)0.1-1.0重量份的亚磷酸三(壬基苯酯)；E) tris(nonylphenyl)phosphite of 0.1-1.0 parts by weight;

F)0.1-1.0重量份的苯甲基硅油；以及F) 0.1-1.0 parts by weight of benzyl silicone oil; and

G)0.4-2.0重量份的钙锌复合稳定剂。G) 0.4-2.0 parts by weight of calcium-zinc composite stabilizer.

7.根据第1-6项中任一项所述的增塑聚氯乙烯材料，包含如下组分：7. The plasticized polyvinyl chloride material according to any one of items 1-6, comprising the following components:

A)100重量份的PVC树脂；A) the PVC resin of 100 parts by weight;

B)30-70重量份的增塑剂；B) the plasticizer of 30-70 parts by weight;

C)5-15重量份的乙烯-醋酸乙烯酯-羰基共聚物；C) 5-15 parts by weight of ethylene-vinyl acetate-carbonyl copolymer;

D)1-5重量份的环氧大豆油；D) the epoxidized soybean oil of 1-5 weight part;

E)0.1-0.5重量份的亚磷酸三(壬基苯酯)；E) tris(nonylphenyl phosphite) of 0.1-0.5 parts by weight;

F)0.1-0.5重量份的苯甲基硅油；以及F) 0.1-0.5 parts by weight of benzyl silicone oil; and

G)0.7-1.5重量份的钙锌复合稳定剂。G) 0.7-1.5 parts by weight of calcium-zinc composite stabilizer.

8.一种制备如第1-7项中任一项所述的增塑聚氯乙烯材料的方法，包括：8. A method for preparing a plasticized polyvinyl chloride material as described in any one of items 1-7, comprising:

1)将PVC树脂和除了组分C以外的其他组分在高速混合机中混合均匀；以及1) mix the PVC resin and other components except component C in a high-speed mixer; and

2)将步骤1)中获得的混合物转移到双辊混炼机上，加入组分C进行混炼，得到增塑聚氯乙烯材料。2) Transfer the mixture obtained in step 1) to a two-roll mixer, add component C for mixing, and obtain a plasticized polyvinyl chloride material.

9.根据第8项所述的方法，其中步骤1)中的混合在85-95℃的温度下进行15-20min；和/或步骤2)中的混炼于155-165℃下进行15-20min。9. The method according to item 8, wherein the mixing in step 1) is carried out at a temperature of 85-95° C. for 15-20 minutes; and/or the mixing in step 2) is carried out at 155-165° C. for 15-20 minutes. 20min.

10.根据第1-7中任一项所述的增塑聚氯乙烯材料在食品包装和医疗器械中的用途，尤其在食品包装袋和膜、输液管、输液袋、输血管、输血袋中的用途。10. Use of the plasticized polyvinyl chloride material according to any one of items 1-7 in food packaging and medical devices, especially in food packaging bags and films, infusion tubes, infusion bags, blood vessels, and blood transfusion bags the use of.

具体实施方式detailed description

根据本发明的一个方面，提供了一种增塑聚氯乙烯材料，其包含如下组分：According to one aspect of the present invention, a kind of plasticized polyvinyl chloride material is provided, and it comprises following components:

A)100重量份的PVC树脂；A) the PVC resin of 100 parts by weight;

B)20-80重量份的一种或多种选自下组的主增塑剂：环己烷-1,2-二甲酸二异辛酯(DEHCH)、环己烷-1,2-二甲酸二异壬酯(DINCH)、柠檬酸三丁酯(TBC)和乙酰柠檬酸三丁酯(ATBC)；以及B) 20-80 parts by weight of one or more main plasticizers selected from the following group: diisooctyl cyclohexane-1,2-dicarboxylate (DEHCH), cyclohexane-1,2-dicarboxylate Diisononyl formate (DINCH), tributyl citrate (TBC), and acetyl tributyl citrate (ATBC); and

C)5-20重量份作为辅增塑剂的乙烯-醋酸乙烯酯-羰基共聚物。C) 5-20 parts by weight of ethylene-vinyl acetate-carbonyl copolymer as a secondary plasticizer.

在本发明中，PVC作为基体材料，对于该材料没有特别的限制，硬质、软质PVC都可使用。In the present invention, PVC is used as the base material, and there is no particular limitation on the material, and both hard and soft PVC can be used.

在本发明的一个优选实施方案中，作为组分A的PVC树脂包含20-40重量％的平均聚合度为1000-1500、尤其为1000-1300的低聚合度PVC树脂和60-80重量％的平均聚合度为2000-2700、尤其为2000-2500的高聚合度PVC树脂，更优选作为组分A的PVC树脂包含20-32重量％的平均聚合度为1000-1500、尤其为1000-1300的低聚合度PVC树脂和68-80重量％的平均聚合度为2000-2700、尤其为2000-2500的高聚合度PVC树脂，基于所述PVC树脂的总重量。在本发明材料中，低聚合度PVC树脂可以改善材料在加工过程中的流动性，降低加工温度，而高聚合度PVC树脂可以使材料的柔软性和弹性得到明显提高。In a preferred embodiment of the present invention, the PVC resin as component A comprises 20-40% by weight of a low-polymerization degree PVC resin with an average degree of polymerization of 1000-1500, especially 1000-1300, and 60-80% by weight of A high degree of polymerization PVC resin with an average degree of polymerization of 2000-2700, especially 2000-2500, more preferably as component A the PVC resin comprises 20-32% by weight of A PVC resin with a low degree of polymerization and 68-80% by weight of a PVC resin with an average degree of polymerization of 2000-2700, especially 2000-2500, based on the total weight of the PVC resin. In the material of the present invention, the PVC resin with a low degree of polymerization can improve the fluidity of the material during processing and reduce the processing temperature, while the PVC resin with a high degree of polymerization can significantly improve the softness and elasticity of the material.

在本发明中，作为组分B的主增塑剂采用DEHCH、DINCH、TBC、ATBC其中的一种或几种。这四种增塑剂都是无毒环保型增塑剂，且极性较大，与PVC相容性很好。In the present invention, one or more of DEHCH, DINCH, TBC, ATBC is used as the main plasticizer of component B. These four plasticizers are all non-toxic and environment-friendly plasticizers with high polarity and good compatibility with PVC.

环己烷羧酸酯类增塑剂比柠檬酸酯类增塑剂具有更优的低温柔软性和耐挥发性，但是增塑效率和热稳定性比柠檬酸酯类增塑剂稍差，将这两类增塑剂复配加入PVC中，可以得到综合性能更加优异的增塑聚氯乙烯材料。因此，对本发明而言优选的是，将DEHCH和/或DINCH与TBC和/或ATBC的组合用作主塑化剂。Cyclohexane carboxylate plasticizers have better low-temperature flexibility and volatility resistance than citrate plasticizers, but their plasticizing efficiency and thermal stability are slightly worse than citrate plasticizers. These two types of plasticizers are compounded and added to PVC to obtain plasticized polyvinyl chloride materials with more excellent comprehensive properties. It is therefore preferred for the present invention to use DEHCH and/or DINCH in combination with TBC and/or ATBC as primary plasticizers.

在本发明增塑聚氯乙烯材料中，每100重量份的PVC树脂，主增塑 剂的含量通常为20-80重量份，优选30-70重量份，特别优选40-60重量份。In the plasticized polyvinyl chloride material of the present invention, per 100 parts by weight of PVC resin, the content of the main plasticizer is usually 20-80 parts by weight, preferably 30-70 parts by weight, particularly preferably 40-60 parts by weight.

在本发明中，采用乙烯-醋酸乙烯酯-羰基共聚物作为辅增塑剂与主增塑剂相结合使用。根据本发明使用的助增塑剂为乙烯-醋酸乙烯酯-羰基三元共聚物(EVACO)，该共聚物的化学结构如下：In the present invention, ethylene-vinyl acetate-carbonyl copolymer is used as the auxiliary plasticizer in combination with the main plasticizer. The auxiliary plasticizer used according to the present invention is ethylene-vinyl acetate-carbonyl terpolymer (EVACO), the chemical structure of this copolymer is as follows:

EVACO是一种高分子量共聚物，在本发明中不仅可增强PVC的韧性和弹性，而且不会像液体增塑剂一样容易迁移渗出。EVACO可通过将一氧化碳与乙烯和醋酸乙烯酯共聚而获得。在EVACO中，乙烯单体单元的含量通常为58-70重量％，醋酸乙烯酯单元的含量通常为20-32重量％，和羰基单元的含量通常为7-15重量％，基于EVACO的总重量。优选的是，在EVACO中，乙烯单体单元的含量通常为60-68重量％，醋酸乙烯酯单元的含量通常为23-30％，和羰基单元的含量通常为8-12重量％，基于EVACO的总重量。EVACO is a high-molecular-weight copolymer, which can not only enhance the toughness and elasticity of PVC in the present invention, but also not easily migrate and seep out like liquid plasticizers. EVACO is obtained by copolymerizing carbon monoxide with ethylene and vinyl acetate. In EVACO, the content of ethylene monomer units is usually 58-70% by weight, the content of vinyl acetate units is usually 20-32% by weight, and the content of carbonyl units is usually 7-15% by weight, based on the total weight of EVACO . Preferably, in EVACO, the content of ethylene monomer units is usually 60-68% by weight, the content of vinyl acetate units is usually 23-30%, and the content of carbonyl units is usually 8-12% by weight, based on EVACO of the total weight.

在本发明的一个特别实施方案中，作为组分C的聚合物改性剂乙烯-醋酸乙烯酯-羰基共聚物，使用来自美国杜邦公司的Elvaloy741型和/或Elvaloy742树脂。In a particular embodiment of the invention, as polymer modifier ethylene-vinyl acetate-carbonyl copolymer of component C, resins of the type Elvaloy 741 and/or Elvaloy 742 from DuPont, USA are used.

在本发明增塑聚氯乙烯材料中，每100重量份的PVC树脂，辅增塑剂EVACO的含量通常为5-20重量份，优选5-15重量份，特别优选7-15重量份。In the plasticized polyvinyl chloride material of the present invention, per 100 parts by weight of PVC resin, the content of auxiliary plasticizer EVACO is usually 5-20 parts by weight, preferably 5-15 parts by weight, particularly preferably 7-15 parts by weight.

在本发明的增塑聚氯乙烯材料中，还可以包含其它常用助剂，例如其它增塑剂，润滑剂，稳定剂，抗氧化剂等。In the plasticized polyvinyl chloride material of the present invention, other common additives may also be included, such as other plasticizers, lubricants, stabilizers, antioxidants and the like.

例如，为了降低成本，本发明材料还可每100重量份PVC包含1-10重量份，优选1-5重量份的环氧大豆油。For example, in order to reduce costs, the material of the present invention may also contain 1-10 parts by weight, preferably 1-5 parts by weight, of epoxidized soybean oil per 100 parts by weight of PVC.

本发明材料还可每100重量份PVC包含0.1-1.0重量份，优选0.1-0.5重量份亚磷酸三(壬基苯酯)作为抗氧剂和防老剂。The material of the present invention may also contain 0.1-1.0 parts by weight, preferably 0.1-0.5 parts by weight, of tris(nonylphenyl phosphite) as antioxidant and anti-aging agent per 100 parts by weight of PVC.

本发明材料还可每100重量份PVC包含0.1-1.0重量份，优选0.1-0.5重量份苯甲基硅油作为润滑剂。The material according to the invention may also contain 0.1-1.0 parts by weight, preferably 0.1-0.5 parts by weight, of benzyl silicone oil as a lubricant per 100 parts by weight of PVC.

本发明材料还可每100重量份PVC包含0.4-2.0重量份，优选0.7-1.5重量份的钙锌复合稳定剂，以抑制PVC在加工时的降解。钙锌复合稳定剂为PVC材料热加工的常用稳定剂，它可以通过将硬脂酸钙和硬脂酸锌与多元醇、亚磷酸酯、β-二酮、沸石和水滑石中的一种或多种复配而得。对于本发明，以硬脂酸钙和硬脂酸锌为主要成分的复合稳定剂都可使用。The material of the present invention may also contain 0.4-2.0 parts by weight, preferably 0.7-1.5 parts by weight, of a calcium-zinc composite stabilizer per 100 parts by weight of PVC, so as to inhibit the degradation of PVC during processing. Calcium-zinc composite stabilizer is a commonly used stabilizer for thermal processing of PVC materials. It can be prepared by combining calcium stearate and zinc stearate with polyols, phosphites, β-diketones, zeolites and hydrotalcites or A variety of compounds obtained. For the present invention, the composite stabilizer with calcium stearate and zinc stearate as main components can be used.

在本发明的一个特别优选实施方案中，本发明的增塑聚氯乙烯材料包含如下组分：In a particularly preferred embodiment of the present invention, the plasticized polyvinyl chloride material of the present invention comprises the following components:

A)100重量份的PVC树脂；A) the PVC resin of 100 parts by weight;

B)30-70重量份的增塑剂；B) the plasticizer of 30-70 parts by weight;

C)5-15重量份的乙烯-醋酸乙烯酯-羰基共聚物；C) 5-15 parts by weight of ethylene-vinyl acetate-carbonyl copolymer;

D)1-5重量份的环氧大豆油；D) the epoxidized soybean oil of 1-5 weight part;

E)0.1-0.5重量份的亚磷酸三(壬基苯酯)；E) tris(nonylphenyl phosphite) of 0.1-0.5 parts by weight;

F)0.1-0.5重量份的苯甲基硅油；以及F) 0.1-0.5 parts by weight of benzyl silicone oil; and

G)0.7-1.5重量份的钙锌复合稳定剂。G) 0.7-1.5 parts by weight of calcium-zinc composite stabilizer.

为了制备本发明的增塑聚氯乙烯材料，本发明还提供了一种制备它的方法。In order to prepare the plasticized polyvinyl chloride material of the present invention, the present invention also provides a method for preparing it.

因此，根据本发明的另一方面，提供了一种制备本发明增塑聚氯乙烯材料的方法，该方法包括：Therefore, according to another aspect of the present invention, there is provided a method for preparing the plasticized polyvinyl chloride material of the present invention, the method comprising:

1)将PVC树脂和除了组分C以外的其他组分在高速混合机中混合均匀；以及1) mix the PVC resin and other components except component C in a high-speed mixer; and

2)将步骤1)中获得的混合物转移到双辊混炼机上，加入组分C进行混炼，得到增塑聚氯乙烯材料。2) Transfer the mixture obtained in step 1) to a two-roll mixer, add component C for mixing, and obtain a plasticized polyvinyl chloride material.

步骤1)将小分子的添加剂与PVC树脂进行预分散，可以防止小分子的添加剂在双辊混炼时发生团聚而导致分散不均。由于组分C的极性较大，将其单独在步骤2)中加入，可以防止小分子的添加剂因组分C的影响而分散不均匀。Step 1) Pre-dispersing the small molecule additives with the PVC resin can prevent the small molecule additives from agglomerating during twin-roll kneading and causing uneven dispersion. Since component C is more polar, it can be added separately in step 2), which can prevent the small molecule additives from being unevenly dispersed due to the influence of component C.

优选的是，步骤1)中的混合在85-95℃的温度下进行15-20min。步骤 2)中的混炼于155-165℃下进行15-20min。Preferably, the mixing in step 1) is carried out at a temperature of 85-95° C. for 15-20 min. The mixing in step 2) is carried out at 155-165°C for 15-20min.

在本发明制备方法的步骤1)中，有利的是，高速混合机的温度为85-95℃，混合时间为15-20min,桨叶转速900-1100rpm。In step 1) of the preparation method of the present invention, it is advantageous that the temperature of the high-speed mixer is 85-95° C., the mixing time is 15-20 minutes, and the blade rotation speed is 900-1100 rpm.

在本发明方法的步骤2)中，有利的是，双辊混炼机的混炼温度为155-165℃，混炼时间为15-20min，辊筒间距1-3mm，辊筒转速40-55rpm。In step 2) of the method of the present invention, advantageously, the mixing temperature of the two-roller mixer is 155-165°C, the mixing time is 15-20min, the distance between the rollers is 1-3mm, and the roller speed is 40-55rpm .

本发明的增塑聚氯乙烯材料具有以下优点：采用了无毒环保型增塑剂，可用于食品包装和医疗器材等领域，对人体没有危害。所选择的增塑剂极性较大，与PVC的相容性好，分散均匀，且在使用过程中不易从材料内部迁出，并且使得材料的加工温度降低到了160℃，相比于DEHP等邻苯二甲酸酯增塑的PVC材料，其具有更优异的低温柔软性、拉伸强度和断裂伸长率等，且加入较少量的增塑剂就能达到较好的性能要求。另外，本发明材料中加入的EVACO型树脂改性剂，是一种高分子共聚物，能够增强PVC的韧性和弹性，而且不会像液体增塑剂一样产生迁移，是一种永久性增塑剂，且对主增塑剂的迁移和抽出起到阻止作用。当本发明的PVC树脂采用高聚合度树脂和低聚合度树脂的混合物且高聚合度树脂作为主体原料时，所得增塑材料的柔软性、弹性和强度都明显较常用的聚氯乙烯材料(聚合度在1050－1100)好，特别是低温性能。本发明的增塑聚氯乙烯还具有优异的透明性，特别适用于一些对透明性有要求的制品。The plasticized polyvinyl chloride material of the invention has the following advantages: it adopts a non-toxic and environment-friendly plasticizer, can be used in fields such as food packaging and medical equipment, and has no harm to human body. The selected plasticizer has high polarity, good compatibility with PVC, uniform dispersion, and is not easy to migrate out of the material during use, and reduces the processing temperature of the material to 160 ° C, compared with DEHP and other Phthalate-plasticized PVC materials have more excellent low-temperature flexibility, tensile strength and elongation at break, etc., and can achieve better performance requirements by adding a small amount of plasticizer. In addition, the EVACO resin modifier added to the material of the present invention is a polymer copolymer, which can enhance the toughness and elasticity of PVC, and will not migrate like a liquid plasticizer, and is a permanent plasticizer. agent, and prevent the migration and extraction of the main plasticizer. When the PVC resin of the present invention adopts the mixture of high polymerization degree resin and low polymerization degree resin and the high polymerization degree resin is as the main raw material, the softness, elasticity and strength of gained plasticized material are all obviously more commonly used polyvinyl chloride material (polymerization) The temperature is 1050-1100) good, especially low temperature performance. The plasticized polyvinyl chloride of the present invention also has excellent transparency, and is especially suitable for some products requiring transparency.

因此，本发明的增塑聚氯乙烯材料特别适合用于食品包装和医疗器材等领域。Therefore, the plasticized polyvinyl chloride material of the present invention is particularly suitable for use in fields such as food packaging and medical equipment.

因此，根据本发明的最后一个方面，提供了本发明的增塑聚氯乙烯材料特在食品包装和医疗器材中的用途，尤其在食品包装袋和膜、输液管、输液袋、输血管、输血袋中的用途。Therefore, according to the last aspect of the present invention, there is provided the use of the plasticized polyvinyl chloride material of the present invention especially in food packaging and medical equipment, especially in food packaging bags and films, infusion tubes, infusion bags, blood transfusion vessels, blood transfusion Uses in bags.

实施例Example

在下述各实施例中，若没有特别说明，各组分含量采用的是重量份数。In the following examples, unless otherwise specified, the content of each component is in parts by weight.

在以下各实施例中，采用以下方法对所得增塑聚氯乙烯材料进行测试：In each of the following examples, the following methods are used to test the plasticized polyvinyl chloride material obtained:

冲击法脆化温度：GB/T5470-2008Shock embrittlement temperature: GB/T5470-2008

冲击强度：GB/T1843-2008，在-30℃下测试。Impact strength: GB/T1843-2008, tested at -30°C.

拉伸性能：GB/T528-1992Tensile properties: GB/T528-1992

硬度：GB/T531-1999Hardness: GB/T531-1999

挥发性：ASTMD1023-94(2003)Volatility: ASTMD1023-94(2003)

实施例1Example 1

将25份平均聚合度为1050的低聚合度PVC树脂、75份聚合度为2400的高聚合度PVC树脂与1.2份的钙锌复合稳定剂(来自上海永研化工科技有限公司的106-8型)先加入高速混合机，开动搅拌，桨叶转速为950rpm，温度升至90℃，保持转速和温度，依次加入45份的DEHCH增塑剂、5份的环氧大豆油、0.4份的亚磷酸三(壬基苯酯)和0.3份的苯甲基硅油，搅拌混合15min后，将混合物转移到双辊混炼机中与10份的Elvaloy741进行混炼，混炼温度控制在165℃，辊筒间距为2min，辊筒转速为55rpm，混炼时间为15min，然后将混炼得到的共混物再经过挤出、造粒、注射制成样品进行测试。25 parts of average degree of polymerization is 1050 low degree of polymerization PVC resin, 75 parts of high degree of polymerization PVC resin of 2400 degree of polymerization and 1.2 parts of calcium-zinc composite stabilizer (106-8 type from Shanghai Yongyan Chemical Technology Co., Ltd. ) into the high-speed mixer first, start stirring, the paddle speed is 950rpm, the temperature rises to 90°C, maintain the speed and temperature, and then add 45 parts of DEHCH plasticizer, 5 parts of epoxy soybean oil, and 0.4 parts of phosphorous acid Tris(nonylphenyl ester) and 0.3 parts of benzyl silicone oil were stirred and mixed for 15 minutes, and then transferred to a two-roller mixer to be mixed with 10 parts of Elvaloy741. The spacing is 2 minutes, the rotating speed of the roller is 55 rpm, and the mixing time is 15 minutes, and then the blend obtained by mixing is extruded, granulated, and injected to make samples for testing.

各测试结果见表1和表2。The test results are shown in Table 1 and Table 2.

实施例2Example 2

重复实施例1，不同之处在于：将平均聚合度为1050的低聚合度PVC树脂改成37份，平均聚合度为2400的高聚合度PVC树脂改成63份。Repeat Example 1, the difference is: the average degree of polymerization is 1050 low polymerization degree of PVC resin into 37 parts, the average degree of polymerization of 2400 high degree of polymerization PVC resin into 63 parts.

各测试结果见表1和表2。The test results are shown in Table 1 and Table 2.

实施例3Example 3

重复实施例1，不同之处在于：将高聚合度PVC替换为平均聚合度2100的PVC。Repeat Example 1, the difference is: PVC with a high degree of polymerization is replaced by PVC with an average degree of polymerization of 2100.

各测试结果见表1和表2。The test results are shown in Table 1 and Table 2.

实施例4Example 4

重复实施例1，不同之处在于：将Elvaloy741的份数改为18份。Repeat Example 1, except that the number of parts of Elvaloy741 is changed to 18 parts.

各测试结果见表1和表2。The test results are shown in Table 1 and Table 2.

对比例5Comparative example 5

重复实施例1，不同之处在于：不加入Elvaloy741。Example 1 was repeated, except that Elvaloy741 was not added.

各测试结果见表1和表2。The test results are shown in Table 1 and Table 2.

实施例6Example 6

重复实施例1，不同之处在于：将45份的DEHCH增塑剂改为20份DEHCH与25份ATBC的混合增塑剂。Repeat Example 1, the difference is: change the 45 parts of DEHCH plasticizer into the mixed plasticizer of 20 parts of DEHCH and 25 parts of ATBC.

各测试结果见表1和表2。The test results are shown in Table 1 and Table 2.

实施例7Example 7

重复实施例1，不同之处在于：将DEHCH的加入量改为70份。Repeat Example 1, the difference is: the addition of DEHCH is changed into 70 parts.

各测试结果见表1和表2。The test results are shown in Table 1 and Table 2.

实施例8Example 8

重复实施例1，不同之处在于：将45份的DEHCH改为15份的DEHCH与15份的ATBC。Repeat Example 1, except that 45 parts of DEHCH are changed to 15 parts of DEHCH and 15 parts of ATBC.

各测试结果见表1和表2。The test results are shown in Table 1 and Table 2.

实施例9Example 9

重复实施例1，不同之处在于：将低聚合度PVC替换为平均聚合度为1450的PVC。Example 1 was repeated, except that PVC with a low degree of polymerization was replaced by PVC with an average degree of polymerization of 1450.

各测试结果见表1和表2。The test results are shown in Table 1 and Table 2.

实施例10Example 10

重复实施例1，不同之处在于：将45份的DEHCH增塑剂改为20份的DINCH和25份的TBC。Repeat Example 1, except that 45 parts of DEHCH plasticizer is changed to 20 parts of DINCH and 25 parts of TBC.

各测试结果见表1和表2。The test results are shown in Table 1 and Table 2.

实施例11Example 11

重复实施例1，不同之处在于：将Elvaloy741的份数改为6份。Repeat Example 1, except that the number of parts of Elvaloy741 is changed to 6 parts.

各测试结果见表1和表2。The test results are shown in Table 1 and Table 2.

实施例12Example 12

重复实施例1，不同之处在于：将45份的DEHCH增塑剂改为45份的ATBC增塑剂。Repeat embodiment 1, difference is: change 45 parts of DEHCH plasticizers into 45 parts of ATBC plasticizers.

各测试结果见表1和表2。The test results are shown in Table 1 and Table 2.

实施例13Example 13

重复实施例1，不同之处在于：100份的PVC树脂全部采用平均聚合度为1100的PVC树脂。Repeat Example 1, the difference is: 100 parts of PVC resin all use PVC resin with an average degree of polymerization of 1100.

各测试结果见表1和表2。The test results are shown in Table 1 and Table 2.

实施例14Example 14

重复实施例1，不同之处在于：100份的PVC树脂全部采用平均聚合度为2400的PVC树脂。Repeat Example 1, the difference is: 100 parts of PVC resin all use PVC resin with an average degree of polymerization of 2400.

各测试结果见表1和表2。The test results are shown in Table 1 and Table 2.

对比例15Comparative example 15

重复实施例12，不同之处在于：不加入Elvaloy741。Example 12 was repeated, except that Elvaloy741 was not added.

各测试结果见表1和表2。The test results are shown in Table 1 and Table 2.

实施例16Example 16

重复实施例1，不同之处在于：不加入环氧大豆油、亚磷酸三(壬基苯酯)和苯甲基硅油。Repeat Example 1, the difference is: do not add epoxidized soybean oil, tris(nonylphenyl phosphite) and phenylmethyl silicone oil.

各测试结果见表1和表2。The test results are shown in Table 1 and Table 2.

表1Table 1

表2Table 2

Claims (23)

1. a kind of plasticised polyvinyl chloride material, which includes following component：

A) the polyvinyl chloride resin of 100 weight portions；

B) the primary plasticizer that one or more of 30-70 weight portions is selected from the group：Hexamethylene -1,2- dioctyl phthalate di-isooctyls(DEHCH), hexamethylene -1,2- dioctyl phthalate dinonyl (DINCH), tributyl citrate (TBC) and tributyl 2-acetylcitrate(ATBC)；And

C) ethylene-vinyl acetate-carbonyl copolymer (EVACO) of the 5-15 weight portions as co-plasticizer.

2. plasticised polyvinyl chloride material according to claim 1, wherein the polyvinyl chloride resin is flat comprising 20-40 weight %Height of the average degree of polymerization of the right PVC resin with low degree of polymerization and 60-80 weight % for 1000-1500 of homopolymerization for 2000-2700Degree of polymerization polyvinyl chloride resin, the gross weight based on the polyvinyl chloride resin.

3. plasticised polyvinyl chloride material according to claim 1, wherein the polyvinyl chloride resin is flat comprising 20-40 weight %Height of the average degree of polymerization of the right PVC resin with low degree of polymerization and 60-80 weight % for 1000-1300 of homopolymerization for 2000-2500Degree of polymerization polyvinyl chloride resin, the gross weight based on the polyvinyl chloride resin.

4. plasticised polyvinyl chloride material according to claim 1, wherein the polyvinyl chloride resin is flat comprising 20-32 weight %Height of the average degree of polymerization of the right PVC resin with low degree of polymerization and 68-80 weight % for 1000-1500 of homopolymerization for 2000-2700Degree of polymerization polyvinyl chloride resin, the gross weight based on the polyvinyl chloride resin.

5. plasticised polyvinyl chloride material according to claim 1, wherein the polyvinyl chloride resin is flat comprising 20-32 weight %Height of the average degree of polymerization of the right PVC resin with low degree of polymerization and 68-80 weight % for 1000-1300 of homopolymerization for 2000-2500Degree of polymerization polyvinyl chloride resin, the gross weight based on the polyvinyl chloride resin.

6. plasticised polyvinyl chloride material according to claim 1, wherein by hexamethylene -1,2- dioctyl phthalate di-isooctyl and/Or the combination modeling of deciding of hexamethylene -1,2- dioctyl phthalate dinonyl and tributyl citrate and/or tributyl 2-acetylcitrateAgent.

7. plasticised polyvinyl chloride material according to claim 2, wherein by hexamethylene -1,2- dioctyl phthalate di-isooctyl and/Or the combination modeling of deciding of hexamethylene -1,2- dioctyl phthalate dinonyl and tributyl citrate and/or tributyl 2-acetylcitrateAgent.

8. plasticised polyvinyl chloride material according to claim 3, wherein by hexamethylene -1,2- dioctyl phthalate di-isooctyl and/Or the combination modeling of deciding of hexamethylene -1,2- dioctyl phthalate dinonyl and tributyl citrate and/or tributyl 2-acetylcitrateAgent.

9. plasticised polyvinyl chloride material according to claim 4, wherein by hexamethylene -1,2- dioctyl phthalate di-isooctyl and/Or the combination modeling of deciding of hexamethylene -1,2- dioctyl phthalate dinonyl and tributyl citrate and/or tributyl 2-acetylcitrateAgent.

10. plasticised polyvinyl chloride material according to claim 5, wherein by hexamethylene -1,2- dioctyl phthalate di-isooctyl and/Or the combination modeling of deciding of hexamethylene -1,2- dioctyl phthalate dinonyl and tributyl citrate and/or tributyl 2-acetylcitrateAgent.

The 11. plasticised polyvinyl chloride materials according to any one of claim 1-10, wherein ethylene-vinyl acetate-In carbonyl copolymer, the content of ethylene monomer unit is 58-70 weight %, and the content of vinyl acetate units is 20-32 weights%, and the content of carbonyl unit are measured for 7-15 weight %, the gross weight based on ethylene-vinyl acetate-carbonyl copolymer.

12. plasticised polyvinyl chloride materials according to claim 11, wherein in ethylene-vinyl acetate-carbonyl copolymerIn, the content of ethylene monomer unit is 60-68 weight %, and the content of vinyl acetate units is 23-30%, and carbonyl unitContent is usually 8-12 weight %, the gross weight based on ethylene-vinyl acetate-carbonyl copolymer.

13. plasticised polyvinyl chloride material according to claim 11, wherein using the Elvaloy741 of du pont companyType and/or Elvaloy742 types resin are used as ethylene-vinyl acetate-carbonyl copolymer.

The 14. plasticised polyvinyl chloride materials according to any one of claim 1-10, the wherein material are based on every 100 weightPrimary plasticizer of the polyvinyl chloride resin included by part comprising 40-60 weight portions and the ethyl vinyl acetate second as co-plasticizer of 7-15 partsAlkene ester-carbonyl copolymer.

15. plasticised polyvinyl chloride materials according to claim 11, the wherein material are included based on every 100 weight portionPrimary plasticizer of the polyvinyl chloride resin comprising 40-60 weight portions and the ethylene-vinyl acetate-carbonyl as co-plasticizer of 7-15 partsCopolymer.

16. plasticised polyvinyl chloride materials according to claim 12, the wherein material are included based on every 100 weight portionPrimary plasticizer of the polyvinyl chloride resin comprising 40-60 weight portions and the ethylene-vinyl acetate-carbonyl as co-plasticizer of 7-15 partsCopolymer.

17. plasticised polyvinyl chloride materials according to claim 13, the wherein material are included based on every 100 weight portionPrimary plasticizer of the polyvinyl chloride resin comprising 40-60 weight portions and the ethylene-vinyl acetate-carbonyl as co-plasticizer of 7-15 partsCopolymer.

The 18. plasticised polyvinyl chloride materials according to any one of claim 1-10, the wherein material are based on every 100 weightThe polyvinyl chloride resin included by part, also comprising following component：

D) the epoxy soybean oil of 1-10 weight portions；

E) the phosphorous acid three (nonyl phenyl ester) of 0.1-1.0 weight portions；

F) the polymethylphenyl siloxane fluid of 0.1-1.0 weight portions；And

G) the calcium-zinc composite stabilizing agent of 0.4-2.0 weight portions.

The 19. plasticised polyvinyl chloride materials according to any one of claim 1-10, comprising following component：

A) the polyvinyl chloride resin of 100 weight portions；

B) the plasticizer of 30-70 weight portions；

C) the ethylene-vinyl acetate of 5-15 weight portions-carbonyl copolymer；

D) the epoxy soybean oil of 1-5 weight portions；

E) the phosphorous acid three (nonyl phenyl ester) of 0.1-0.5 weight portions；

F) the polymethylphenyl siloxane fluid of 0.1-0.5 weight portions；And

G) the calcium-zinc composite stabilizing agent of 0.7-1.5 weight portions.

A kind of 20. methods of the plasticised polyvinyl chloride material prepared as any one of claim 1-19, including：

1) mix homogeneously in high-speed mixer by polyvinyl chloride resin and other components in addition to component C；And

2) by step 1) in obtain mixture be transferred on double roll mill, add component C kneaded, obtain plasticising polychlorostyreneVinyl material.

21. methods according to claim 20, wherein step 1) in be blended at a temperature of 85-95 DEG C and carry out 15-20min；And/or step 2) in mixing 15-20min is carried out at 155-165 DEG C.

The 22. plasticised polyvinyl chloride materials according to any one of claim 1-19 are in packaging for foodstuff and medical apparatus and instrumentsPurposes.

23. purposes according to claim 22 are the plasticised polyvinyl chloride material in food pack and film, transfusionPurposes in pipe, transfusion bag, blood transfusion tube, transfusion bags.