技术领域technical field
本发明涉及一种接枝共聚物及其制备方法和其在增容剂中的应用，属于高分子领域。The invention relates to a graft copolymer, a preparation method thereof and an application thereof in compatibilizers, belonging to the field of macromolecules.
背景技术Background technique
聚烯烃嵌段共聚物是由聚丙烯(PP)与聚乙烯(PE)制得的嵌段共聚物，是热塑性弹性体的一种，它与聚烯烃塑料都有一定的相容性，一般用作聚烯烃类改性材料的增韧剂。然而，烯烃嵌段共聚物属于非极性材料，在聚烯烃与极性材料进行共混改性时，烯烃嵌段共聚物只能充当增韧剂不能充当相容剂，这样使得改性效果较差。Polyolefin block copolymer is a block copolymer made of polypropylene (PP) and polyethylene (PE). It is a kind of thermoplastic elastomer. It has certain compatibility with polyolefin plastics. It is generally used As a toughening agent for polyolefin modified materials. However, olefin block copolymers are non-polar materials. When polyolefins and polar materials are blended and modified, olefin block copolymers can only act as tougheners and not as compatibilizers, which makes the modification effect relatively weak. Difference.
增容方式最常见方法是添加两亲相容剂，主要包括嵌段/接枝共聚物，现有的增容剂包括利用PP-PE嵌段共聚物增容PP/PE共混物、PP-g-MAH或PP-g-GEM增容PP/PE共混物和PP/PET共混物、PE-g-MAH增容PP/PE共混物和PE/PET共混物或SEBS-g-MAH增容PE/PET共混物和PP/PET共混物。The most common method of compatibilization is to add amphiphilic compatibilizers, mainly including block/graft copolymers. The existing compatibilizers include using PP-PE block copolymers to compatibilize PP/PE blends, PP- g-MAH or PP-g-GEM compatibilized PP/PE blends and PP/PET blends, PE-g-MAH compatibilized PP/PE blends and PE/PET blends or SEBS-g- MAH compatibilized PE/PET blends and PP/PET blends.
此外，目前高分子增容领域仅限于二元高分子合金增容，对于三元及以上高分子混合体系，由于过于复杂，尚无有效增容剂的报道。In addition, the current field of polymer compatibilization is limited to the compatibilization of binary polymer alloys. For ternary and higher polymer hybrid systems, there are no reports of effective compatibilizers due to their complexity.
发明内容Contents of the invention
针对上述缺陷，本发明提供一种新型的可用作增容剂的接枝共聚物，其是将聚对苯二甲酸乙二醇酯(PET)和/或糖类化合物接枝到聚烯烃嵌段共聚物中制得的可用作增容剂的新型共聚物；所得共聚物能够提高一次性三元共混塑料(如PE、PP和PET三元塑料共混)之间的相容性，通过聚烯烃嵌段共聚物接枝PET，极性获得增强，使得其侧链与共混物中的PET进行共结晶或本体纠缠；通过聚烯烃嵌段共聚物接枝糖类化合物，使得增容剂的糖类化合物侧链与共混物中的PET进行酯交换反应或氢键连接，并且增强增容剂或增容共混物的生物降解性。In view of the above-mentioned defects, the present invention provides a novel graft copolymer that can be used as a compatibilizer, which is grafted polyethylene terephthalate (PET) and/or sugar compounds onto polyolefin embeddings. A new type of copolymer that can be used as a compatibilizer prepared in a block copolymer; the resulting copolymer can improve the compatibility between disposable ternary blend plastics (such as PE, PP and PET ternary plastic blends), By grafting PET with polyolefin block copolymer, the polarity is enhanced, making its side chains co-crystallize or entangle with PET in the blend; grafting sugar compounds with polyolefin block copolymer makes the compatibilizer The side chains of the saccharide compounds in the blend undergo transesterification or hydrogen bonding with the PET in the blend, and enhance the biodegradability of the compatibilizer or the compatibilizer blend.
本发明的技术方案：Technical scheme of the present invention:
本发明要解决的第一个技术问题是提供一种接枝共聚物的制备方法，所述制备方法为：以聚烯烃嵌段共聚物、PET和糖类化合物为原料，在引发剂的作用下将PET和/或糖类化合物接枝到聚烯烃嵌段共聚物中制得所述接枝共聚物；其中，所述聚烯烃嵌段共聚物、PET和糖类化合物的比例为：聚烯烃嵌段共聚物100重量份，PET 0～20重量份，糖类化合物0～20重量份，引发剂0.2～2重量份；并且PET和糖类化合物的用量不能同时为0。The first technical problem to be solved by the present invention is to provide a preparation method of a graft copolymer. The preparation method is: using polyolefin block copolymer, PET and carbohydrate compounds as raw materials, under the action of an initiator, Grafting PET and/or sugar compounds into polyolefin block copolymers to obtain the graft copolymer; wherein, the ratio of the polyolefin block copolymers, PET and sugar compounds is: polyolefin block copolymers 100 parts by weight of segment copolymer, 0-20 parts by weight of PET, 0-20 parts by weight of sugar compound, 0.2-2 parts by weight of initiator; and the amount of PET and sugar compound cannot be 0 at the same time.
进一步，所述聚烯烃嵌段共聚物、PET和糖类化合物的比例为：聚烯烃嵌段共聚物100重量份，PET 1～20重量份，糖类化合物0～20重量份，引发剂0.2～2重量份。Further, the ratio of the polyolefin block copolymer, PET and sugar compound is: 100 parts by weight of polyolefin block copolymer, 1-20 parts by weight of PET, 0-20 parts by weight of sugar compound, and 0.2-20 parts by weight of initiator. 2 parts by weight.
进一步，所述聚烯烃嵌段共聚物、PET和糖类化合物的比例为：聚烯烃嵌段共聚物100重量份，PET 0～20重量份，糖类化合物1～20重量份，引发剂0.2～2重量份。Further, the ratio of the polyolefin block copolymer, PET and sugar compound is: 100 parts by weight of polyolefin block copolymer, 0-20 parts by weight of PET, 1-20 parts by weight of sugar compound, 0.2-20 parts by weight of initiator 2 parts by weight.
进一步，所述聚烯烃嵌段共聚物、PET和糖类化合物的比例为：聚烯烃嵌段共聚物100重量份，PET 1～20重量份，糖类化合物1～20重量份，引发剂0.2～2重量份。Further, the ratio of the polyolefin block copolymer, PET and sugar compound is: 100 parts by weight of polyolefin block copolymer, 1-20 parts by weight of PET, 1-20 parts by weight of sugar compound, 0.2-20 parts by weight of initiator 2 parts by weight.
进一步，所述聚烯烃嵌段共聚物为PP-PE多嵌段共聚物，优选为PP-PE二嵌段共聚物。Further, the polyolefin block copolymer is a PP-PE multi-block copolymer, preferably a PP-PE di-block copolymer.
进一步，所述糖类化合物为聚多糖、低聚糖或单糖。Further, the carbohydrate compound is polysaccharide, oligosaccharide or monosaccharide.
更进一步，所述聚多糖选自：淀粉、壳聚糖、纤维素、海藻酸或海藻酸盐等。Furthermore, the polysaccharide is selected from: starch, chitosan, cellulose, alginic acid or alginate and the like.
更进一步，所述低聚糖选自：二糖、三糖或四糖等。Furthermore, the oligosaccharides are selected from: disaccharides, trisaccharides or tetrasaccharides and the like.
更进一步，所述单糖选自：葡萄糖、果糖、半乳糖或核糖等。Further, the monosaccharide is selected from: glucose, fructose, galactose or ribose and the like.
进一步，所述引发剂为过氧化二异丙苯、过氧化二叔丁基或硝酸铈铵等。Further, the initiator is dicumyl peroxide, di-tert-butyl peroxide or ammonium cerium nitrate.
进一步，所述制备方法为：先将聚烯烃嵌段共聚物、PET和糖类化合物分别溶解或溶胀在溶剂中，然后在引发剂的作用下，于100～140℃下反应2～6h，经冷却析出、抽滤，然后在60～80℃下干燥8～12h干燥制得所述聚合物。Further, the preparation method is as follows: firstly dissolve or swell polyolefin block copolymer, PET and sugar compound in a solvent respectively, then react at 100-140°C for 2-6 hours under the action of an initiator, and Precipitation by cooling, suction filtration, and drying at 60-80°C for 8-12 hours to obtain the polymer.
进一步，所述溶剂为四氯乙烷。Further, the solvent is tetrachloroethane.
进一步，所述聚合物的制备方法包括如下步骤：Further, the preparation method of the polymer comprises the following steps:
(1)将聚烯烃嵌段共聚物、PET和糖类化合物除湿干燥，然后分别于100～140℃在溶剂中充分溶解或溶胀；(1) Dehumidify and dry the polyolefin block copolymer, PET and sugar compounds, and then fully dissolve or swell in the solvent at 100-140°C respectively;
(2)在溶解好的聚烯烃嵌段共聚物中加入部分引发剂，于100～140℃下反应10～30min后加入溶解好的PET，并在该温度下反应2～4h；然后加入剩余的引发剂和溶解好的糖类化合物，继续反应2～4h；(2) Add part of the initiator to the dissolved polyolefin block copolymer, react at 100-140°C for 10-30 minutes, then add the dissolved PET, and react at this temperature for 2-4 hours; then add the remaining The initiator and the dissolved sugar compound continue to react for 2 to 4 hours;
(3)将步骤(2)所得产品倒入低沸点溶剂中冷却析出，并抽滤；随后在60～80℃下烘干8～12h得所述聚合物。(3) Pour the product obtained in step (2) into a low-boiling solvent to cool and precipitate, and suction filter; then dry at 60-80° C. for 8-12 hours to obtain the polymer.
进一步，步骤(3)中，所述低沸点溶剂为：二氯甲烷、石油醚或无水乙醇。Further, in step (3), the low boiling point solvent is: dichloromethane, petroleum ether or absolute ethanol.
本发明要解决的第二个技术问题是提供一种接枝共聚物，其采用上述方法制得。The second technical problem to be solved by the present invention is to provide a graft copolymer prepared by the above method.
进一步，所述聚合物的结构为：Further, the structure of the polymer is:
本发明要解决的第三个技术问题是指出上述接枝共聚物用于聚烯烃共混材料的增溶剂；即本发明所得接枝共聚物可用于改善非极性聚烯烃与极性聚合物之间的相容性。The third technical problem to be solved in the present invention is to point out that the above-mentioned graft copolymer is used as a solubilizer for polyolefin blend materials; compatibility between them.
进一步，用于PP、PE和PET共混材料的增容剂。Further, it is used as a compatibilizer for PP, PE and PET blend materials.
本发明的有益效果：Beneficial effects of the present invention:
本发明将聚对苯二甲酸乙二醇酯(PET)和/或糖类化合物在引发剂的作用下接枝到聚烯烃嵌段共聚物中制得了一种可用作增容剂的新型接枝共聚物；所得接枝共聚物可明显改善非极性聚烯烃与极性聚合物之间的相容性。可见，本发明利用低成本原料制备了可降解增容剂，可增强一次性共混塑料的相容性，提高复合材料的综合性能，降低塑料回收时分类的工作难度，同时促进经济循环。In the present invention, polyethylene terephthalate (PET) and/or sugar compounds are grafted into polyolefin block copolymers under the action of an initiator to obtain a novel graft that can be used as a compatibilizer. graft copolymers; the resulting graft copolymers can significantly improve the compatibility between non-polar polyolefins and polar polymers. It can be seen that the present invention uses low-cost raw materials to prepare a degradable compatibilizer, which can enhance the compatibility of disposable blended plastics, improve the comprehensive performance of composite materials, reduce the difficulty of sorting plastic recycling, and promote economic circulation at the same time.
附图说明：Description of drawings:
图1为本发明用作增容剂的接枝共聚物的合成反应示意图。Figure 1 is a schematic diagram of the synthesis reaction of the graft copolymer used as a compatibilizer in the present invention.
图2为实施例1～7所得产物的红外光谱图。Fig. 2 is the infrared spectrogram of the product obtained in Examples 1-7.
图3为本发明实施例所得聚合物的核磁氢谱图。Fig. 3 is the H NMR spectrum of the polymer obtained in the embodiment of the present invention.
具体实施方式Detailed ways
本发明将聚对苯二甲酸乙二醇酯(PET)和/或糖类化合物接枝到聚烯烃嵌段共聚物中制得的可用作增容剂的新型共聚物；所得共聚物能够提高一次性三元共混塑料(如PE、PP和PET三元塑料共混)之间的相容性，通过聚烯烃嵌段共聚物接枝PET，极性获得增强，使得其侧链与共混物中的PET进行共结晶或本体纠缠；通过聚烯烃嵌段共聚物接枝糖类化合物，使得增容剂的糖类化合物侧链与共混物中的PET进行酯交换反应或氢键连接，并且增强增容剂或增容共混物的生物降解性；即本发明所得共聚物能提高复合材料的韧性和刚度。The present invention grafts polyethylene terephthalate (PET) and/or carbohydrate compound into the novel copolymer that can be used as compatibilizer that makes in polyolefin block copolymer; Gained copolymer can improve Compatibility between disposable ternary blend plastics (such as PE, PP and PET ternary plastic blends), by grafting PET with polyolefin block copolymers, the polarity is enhanced, making its side chains and blends The PET in the blend is co-crystallized or bulk entangled; the sugar compound is grafted by polyolefin block copolymer, so that the side chain of the sugar compound in the compatibilizer is transesterified or hydrogen-bonded with the PET in the blend, and enhanced The biodegradability of the compatibilizer or the compatibilizer blend; that is, the obtained copolymer of the present invention can improve the toughness and rigidity of the composite material.
下面结合实施例对本发明的具体实施方式做进一步的描述，并不因此将本发明限制在所述的实例范围之中。The specific implementation of the present invention will be further described below in conjunction with the examples, and the present invention is not limited to the scope of the examples.
实施例1Example 1
一种三元共混塑料用增容剂的制备方法：A preparation method of a compatibilizer for ternary blend plastics:
称量干燥好的原料PP-PE二嵌段共聚物(牌号：D5545.00)10克、PET(牌号：WB-8816)0.6克和糖类化合物玉米淀粉0.4克，将原料分别在70ml、20ml、15ml的四氯乙烷中溶解或溶胀，溶解温度分别为120℃、140℃、90℃，溶解时间为1-2h。Weigh 10 grams of dried raw materials PP-PE diblock copolymer (brand: D5545.00), 0.6 grams of PET (brand: WB-8816) and 0.4 grams of sugar compound cornstarch, and mix the raw materials in 70ml and 20ml respectively , Dissolve or swell in 15ml of tetrachloroethane, the dissolution temperature is 120°C, 140°C, 90°C respectively, and the dissolution time is 1-2h.
在溶解好的PP-PE二嵌段共聚物中加入0.06克引发剂硝酸铈铵，在130℃反应10min；随后加入溶解好的PET，反应2h后加入0.04克的引发剂硝酸铈铵，再加入溶解好的糖类化合物，反应2h。将产品倒入二氯甲烷中冷却析出并抽滤，随后在60℃下烘干8-12h得目标产物(SBP，红外光谱图如图2)。Add 0.06 g of initiator cerium ammonium nitrate to the dissolved PP-PE diblock copolymer, and react at 130°C for 10 minutes; then add dissolved PET, add 0.04 g of initiator cerium ammonium nitrate after 2 hours of reaction, and then add Dissolved saccharides were reacted for 2 hours. Pour the product into dichloromethane to cool it down and filter it with suction, then dry it at 60°C for 8-12 hours to obtain the target product (SBP, infrared spectrum as shown in Figure 2).
实施例2Example 2
一种三元共混塑料用生物降解性增容剂的制备方法：A preparation method of a biodegradable compatibilizer for ternary blend plastics:
在实施例1的基础上，体系调整为PP-PE二嵌段共聚物10克、PET 0.6克和糖类化合物玉米淀粉0.8克，将原料分别在70ml、20ml、25ml的四氯乙烷中溶解；溶解温度为120℃、140℃、90℃，溶解时间为1-2h。On the basis of Example 1, the system is adjusted to 10 grams of PP-PE diblock copolymer, 0.6 grams of PET and 0.8 grams of sugar compound cornstarch, and the raw materials are dissolved in 70ml, 20ml, and 25ml of tetrachloroethane respectively ; The dissolution temperature is 120°C, 140°C, 90°C, and the dissolution time is 1-2h.
在溶解好的PP-PE二嵌段共聚物中加入0.06克引发剂硝酸铈铵，在130℃反应10min，随后加入溶解好的PET，反应2h后加入0.08克的引发剂硝酸铈铵，再加入溶解好的糖类化合物，反应2h。将产品倒入二氯甲烷中冷却析出并抽滤，随后60℃下烘干8-12h得目标产物(SBP，见图2)。Add 0.06 g of initiator cerium ammonium nitrate to the dissolved PP-PE diblock copolymer, react at 130°C for 10 minutes, then add dissolved PET, add 0.08 g of initiator cerium ammonium nitrate after 2 hours of reaction, and then add Dissolved saccharides were reacted for 2 hours. Pour the product into dichloromethane to cool it down and filter it with suction, then dry it at 60°C for 8-12 hours to obtain the target product (SBP, see Figure 2).
实施例3Example 3
一种三元共混塑料用生物降解性增容剂的制备方法：A preparation method of a biodegradable compatibilizer for ternary blend plastics:
在实施例2的基础上，体系调整为PP-PE二嵌段共聚物10克、PET 0.6克和糖类化合物玉米淀粉1.2克，将原料分别在70ml、20ml、30ml的四氯乙烷中溶解或溶胀；溶解温度为120℃、140℃、90℃，溶解时间为1-2h。On the basis of Example 2, the system is adjusted to 10 grams of PP-PE diblock copolymer, 0.6 grams of PET and 1.2 grams of sugar compound cornstarch, and the raw materials are dissolved in 70ml, 20ml, and 30ml of tetrachloroethane respectively or swelling; the dissolution temperature is 120°C, 140°C, 90°C, and the dissolution time is 1-2h.
在溶解好的PP-PE二嵌段共聚物中加入0.06克引发剂硝酸铈铵，在130℃反应10min，随后加入溶解好的PET，反应2h后加入0.12克的引发剂硝酸铈铵，再加入溶解好的糖类化合物，反应2h。将产品倒入二氯甲烷中冷却析出并抽滤，随后在60℃下烘干8-12h得目标产物(SBP，见图2)。Add 0.06 g of initiator cerium ammonium nitrate to the dissolved PP-PE diblock copolymer, react at 130°C for 10 minutes, then add dissolved PET, add 0.12 g of initiator cerium ammonium nitrate after 2 hours of reaction, and then add Dissolved saccharides were reacted for 2 hours. Pour the product into dichloromethane to cool it down and filter it with suction, then dry it at 60°C for 8-12 hours to obtain the target product (SBP, see Figure 2).
实施例4Example 4
一种三元共混塑料用生物降解性增容剂的制备方法：A preparation method of a biodegradable compatibilizer for ternary blend plastics:
在实施例1的基础上，体系调整为PP-PE二嵌段共聚物10克、PET 0.9克和糖类化合物玉米淀粉0.4克，将原料分别在70ml、25ml、15ml的四氯乙烷中溶解；溶解温度为120℃、140℃、90℃，溶解时间为1-2h。On the basis of Example 1, the system is adjusted to 10 grams of PP-PE diblock copolymer, 0.9 grams of PET and 0.4 grams of sugar compound cornstarch, and the raw materials are dissolved in 70ml, 25ml, and 15ml of tetrachloroethane respectively ; The dissolution temperature is 120°C, 140°C, 90°C, and the dissolution time is 1-2h.
在溶解好的PP-PE二嵌段共聚物中加入0.09克引发剂硝酸铈铵，在130℃反应10min，随后加入溶解好的PET，反应2h后加入0.04克的引发剂硝酸铈铵，再加入溶解好的糖类化合物，反应2h。将产品倒入二氯甲烷中冷却析出并抽滤，随后在60℃下烘干8-12h得目标产物(SBP，见图2)。Add 0.09 grams of initiator cerium ammonium nitrate to the dissolved PP-PE diblock copolymer, react at 130°C for 10 minutes, then add dissolved PET, add 0.04 grams of initiator cerium ammonium nitrate after 2 hours of reaction, and then add Dissolved saccharides were reacted for 2 hours. Pour the product into dichloromethane to cool it down and filter it with suction, then dry it at 60°C for 8-12 hours to obtain the target product (SBP, see Figure 2).
实施例5Example 5
一种三元共混塑料用生物降解性增容剂的制备方法：A preparation method of a biodegradable compatibilizer for ternary blend plastics:
在实施例1的基础上，体系调整为PP-PE二嵌段共聚物10克、PET 1.2克和玉米淀粉0.4克，将原料分别在70ml、30ml、15ml的四氯乙烷中溶解。溶解温度为120℃、140℃、90℃，溶解时间为1-2h。On the basis of Example 1, the system was adjusted to 10 grams of PP-PE diblock copolymer, 1.2 grams of PET and 0.4 grams of corn starch, and the raw materials were dissolved in 70ml, 30ml and 15ml of tetrachloroethane respectively. The dissolution temperature is 120°C, 140°C, 90°C, and the dissolution time is 1-2h.
在溶解好的PP-PE二嵌段共聚物中加入0.12克引发剂硝酸铈铵，在130℃反应10min，随后加入溶解好的PET，反应2h后加入0.04克的引发剂硝酸铈铵，再加入溶解好的玉米淀粉，反应2h。将产品倒入二氯甲烷中冷却析出并抽滤，随后在60℃下烘干8-12h得目标产物(SBP，见图2)。Add 0.12 g of initiator cerium ammonium nitrate to the dissolved PP-PE diblock copolymer, react at 130°C for 10 minutes, then add dissolved PET, add 0.04 g of initiator cerium ammonium nitrate after 2 hours of reaction, and then add The dissolved corn starch was reacted for 2 hours. Pour the product into dichloromethane to cool it down and filter it with suction, then dry it at 60°C for 8-12 hours to obtain the target product (SBP, see Figure 2).
实施例6Example 6
一种三元共混塑料用增容剂的制备方法：A preparation method of a compatibilizer for ternary blend plastics:
在实施例1的基础上，体系调整为PP-PE二嵌段共聚物10克、PET 0.6克，将原料分别在70ml、20ml的四氯乙烷中溶解。溶解温度为120℃、140℃，溶解时间为1-2h。On the basis of Example 1, the system was adjusted to 10 grams of PP-PE diblock copolymer and 0.6 grams of PET, and the raw materials were dissolved in 70 ml and 20 ml of tetrachloroethane respectively. The dissolution temperature is 120°C and 140°C, and the dissolution time is 1-2h.
在溶解好的PP-PE二嵌段共聚物中加入0.06克引发剂硝酸铈铵，在130℃反应10min，随后加入溶解好的PET反应2h，再将产品倒入二氯甲烷中冷却析出并抽滤，随后60℃下烘干8-12h得目标产物(BP，见图2)。Add 0.06 g of initiator cerium ammonium nitrate to the dissolved PP-PE diblock copolymer, react at 130°C for 10 minutes, then add dissolved PET to react for 2 hours, then pour the product into dichloromethane to cool and precipitate and pump Filter, then dry at 60°C for 8-12h to obtain the target product (BP, see Figure 2).
实施例7Example 7
一种三元共混塑料用增容剂的制备方法：A preparation method of a compatibilizer for ternary blend plastics:
称量干燥好的原料PP-PE二嵌段共聚物10克和玉米淀粉0.4克，将原料分别在70ml、15ml的四氯乙烷中溶解或溶胀，溶解温度为120℃、90℃，溶解时间为1-2h。Weigh 10 grams of dried raw materials PP-PE diblock copolymer and 0.4 grams of corn starch, dissolve or swell the raw materials in 70ml and 15ml of tetrachloroethane respectively, the dissolution temperature is 120°C, 90°C, the dissolution time 1-2h.
在溶解好的PP-PE二嵌段共聚物中加入0.04克引发剂硝酸铈铵，在130℃反应10min，再加入溶胀好的玉米淀粉，反应2h。将产品倒入二氯甲烷中冷却析出并抽滤，随后在60℃下烘干8-12h得目标产物(BS，见图2)。Add 0.04 g of initiator cerium ammonium nitrate to the dissolved PP-PE diblock copolymer, react at 130° C. for 10 min, then add swollen cornstarch, and react for 2 h. Pour the product into dichloromethane to cool it down and filter it with suction, then dry it at 60°C for 8-12 hours to obtain the target product (BS, see Figure 2).
实施例8Example 8
一种三元共混塑料用增容剂的制备方法：A preparation method of a compatibilizer for ternary blend plastics:
称量干燥好的原料PP-PE二嵌段共聚物10克和葡萄糖0.4克，将原料分别在70ml、15ml的四氯乙烷中溶解或溶胀，溶解温度为120℃、90℃，溶解时间为1-2h。Weigh 10 grams of dried raw materials PP-PE diblock copolymer and 0.4 grams of glucose, dissolve or swell the raw materials in 70ml and 15ml of tetrachloroethane respectively, the dissolution temperature is 120°C, 90°C, and the dissolution time is 1-2h.
在溶解好的PP-PE二嵌段共聚物中加入0.04克引发剂硝酸铈铵，在130℃反应10min，再加入溶胀好的葡萄糖，反应2h。将产品倒入二氯甲烷中冷却析出并抽滤，随后在60℃下烘干8-12h得目标产物。Add 0.04 g of initiator cerium ammonium nitrate to the dissolved PP-PE diblock copolymer, react at 130° C. for 10 min, then add swollen glucose, and react for 2 h. Pour the product into dichloromethane to cool it down and filter it with suction, then dry it at 60°C for 8-12 hours to obtain the target product.
试验例1Test example 1
三元共混塑料增容测试方法。Test method for compatibilization of ternary blend plastics.
称取干燥好的PP 41份，PE 30份，PET 29份，取实施例1制得的增容剂4份，将其通过物理搅拌均匀，然后加入双螺杆挤出机中进行熔融共混。共混物在255-260℃下以10-20rpm的速度共混5min。随后在250-255℃下注塑成哑铃状的样条，模具温度为25-40℃。然后在1mm/min的速率进行拉伸测试，测得其断裂伸长率为641％，弹性模量为512MPa。各试验例和对比例的原料比例和性能结果如表1所示。Weigh 41 parts of dried PP, 30 parts of PE, 29 parts of PET, and take 4 parts of the compatibilizer prepared in Example 1, stir them uniformly by physical, and then add them into a twin-screw extruder for melt blending. The blend was blended at 255-260 °C for 5 min at a speed of 10-20 rpm. Subsequently, it is injection molded into dumbbell-shaped splines at 250-255° C., and the mold temperature is 25-40° C. Then a tensile test was carried out at a speed of 1 mm/min, and the measured elongation at break was 641%, and the modulus of elasticity was 512 MPa. The raw material ratio and performance results of each test example and comparative example are shown in Table 1.
试验例2Test example 2
称取干燥好的PP 41份，PE 30份，PET 29份，取实施例2制得的增容剂4份，将其通过物理搅拌均匀，然后加入双螺杆挤出机中进行熔融共混。共混物在255-260℃下以10-20rpm的速度共混5min。随后在250-255℃下注塑成哑铃状的样条，模具温度为25-40℃。然后在1mm/min的速率进行拉伸测试，测得其断裂伸长率为498％，弹性模量为474MPa。Weigh 41 parts of dried PP, 30 parts of PE, 29 parts of PET, take 4 parts of the compatibilizer prepared in Example 2, stir them evenly by physical, and then add them into a twin-screw extruder for melt blending. The blend was blended at 255-260 °C for 5 min at a speed of 10-20 rpm. Subsequently, it is injection molded into dumbbell-shaped splines at 250-255° C., and the mold temperature is 25-40° C. Then tensile test was carried out at a rate of 1 mm/min, and the elongation at break was measured to be 498%, and the modulus of elasticity was 474 MPa.
试验例3Test example 3
称取干燥好的PP 41份，PE 30份，PET 29份，取实施例3制得的增容剂4份，将其通过物理搅拌均匀，然后加入双螺杆挤出机中进行熔融共混。共混物在255-260℃下以10-20rpm的速度共混5min。随后在250-255℃下注塑成哑铃状的样条，模具温度为25-40℃。然后在1mm/min的速率进行拉伸测试，测得其断裂伸长率为395％，弹性模量为476MPa。Weigh 41 parts of dried PP, 30 parts of PE, 29 parts of PET, take 4 parts of the compatibilizer prepared in Example 3, stir them uniformly by physical means, and then put them into a twin-screw extruder for melt blending. The blend was blended at 255-260 °C for 5 min at a speed of 10-20 rpm. Subsequently, it is injection molded into dumbbell-shaped splines at 250-255° C., and the mold temperature is 25-40° C. Then tensile test was carried out at a speed of 1 mm/min, and the measured elongation at break was 395%, and the modulus of elasticity was 476 MPa.
试验例4Test example 4
称取干燥好的PP 41份，PE 30份，PET 29份，取实施例4制得的增容剂4份，将其通过物理搅拌均匀，然后加入双螺杆挤出机中进行熔融共混。共混物在255-260℃下以10-20rpm的速度共混5min。随后在250-255℃下注塑成哑铃状的样条，模具温度为25-40℃。然后在1mm/min的速率进行拉伸测试，测得其断裂伸长率为667％，弹性模量为487MPa。Weigh 41 parts of dried PP, 30 parts of PE, 29 parts of PET, and take 4 parts of the compatibilizer prepared in Example 4, stir them uniformly by physical means, and then add them into a twin-screw extruder for melt blending. The blend was blended at 255-260 °C for 5 min at a speed of 10-20 rpm. Subsequently, it is injection molded into dumbbell-shaped splines at 250-255° C., and the mold temperature is 25-40° C. Then a tensile test was carried out at a speed of 1mm/min, and the elongation at break was measured to be 667%, and the modulus of elasticity was 487MPa.
试验例5Test example 5
称取干燥好的PP 41份，PE 30份，PET 29份，取实施例5制得的增容剂4份，将其通过物理搅拌均匀，然后加入双螺杆挤出机中进行熔融共混。共混物在255-260℃下以10-20rpm的速度共混5min。随后在250-255℃下注塑成哑铃状的样条，模具温度为25-40℃。然后在1mm/min的速率进行拉伸测试，测得其断裂伸长率为646％，弹性模量为448MPa。Weigh 41 parts of dried PP, 30 parts of PE, 29 parts of PET, take 4 parts of the compatibilizer prepared in Example 5, stir them uniformly by physical, and then add them into a twin-screw extruder for melt blending. The blend was blended at 255-260 °C for 5 min at a speed of 10-20 rpm. Subsequently, it is injection molded into dumbbell-shaped splines at 250-255° C., and the mold temperature is 25-40° C. Then a tensile test was carried out at a rate of 1mm/min, and the measured elongation at break was 646%, and the modulus of elasticity was 448MPa.
试验例6Test example 6
称取干燥好的PP 41份，PE 30份，PET 29份，取实施例6制得的增容剂4份，将其通过物理搅拌均匀，然后加入双螺杆挤出机中进行熔融共混。共混物在255-260℃下以10-20rpm的速度共混5min。随后在250-255℃下注塑成哑铃状的样条，模具温度为25-40℃。然后在1mm/min的速率进行拉伸测试，测得其断裂伸长率为150％，弹性模量为457MPa。Weigh 41 parts of dried PP, 30 parts of PE, 29 parts of PET, take 4 parts of the compatibilizer prepared in Example 6, stir them uniformly through physical stirring, and then put them into a twin-screw extruder for melt blending. The blend was blended at 255-260 °C for 5 min at a speed of 10-20 rpm. Subsequently, it is injection molded into dumbbell-shaped splines at 250-255° C., and the mold temperature is 25-40° C. Then tensile test was carried out at a rate of 1mm/min, and the measured elongation at break was 150%, and the modulus of elasticity was 457MPa.
试验例7Test Example 7
称取干燥好的PP 41份，PE 30份，PET 29份，取实施例7制得的增容剂4份，将其通过物理搅拌均匀，然后加入双螺杆挤出机中进行熔融共混。共混物在255-260℃下以10-20rpm的速度共混5min。随后在250-255℃下注塑成哑铃状的样条，模具温度为25-40℃。然后在1mm/min的速率进行拉伸测试，测得其断裂伸长率为610％，弹性模量为467MPa。Weigh 41 parts of dried PP, 30 parts of PE, 29 parts of PET, take 4 parts of the compatibilizer prepared in Example 7, stir them uniformly by physical, and then add them into a twin-screw extruder for melt blending. The blend was blended at 255-260 °C for 5 min at a speed of 10-20 rpm. Subsequently, it is injection molded into dumbbell-shaped splines at 250-255° C., and the mold temperature is 25-40° C. Then a tensile test was carried out at a rate of 1 mm/min, and the measured elongation at break was 610%, and the modulus of elasticity was 467 MPa.
试验例8Test example 8
称取干燥好的PP 41份，PE 30份，PET 29份，取实施例8制得的增容剂4份，将其通过物理搅拌均匀，然后加入双螺杆挤出机中进行熔融共混。共混物在255-260℃下以10-20rpm的速度共混5min。随后在250-255℃下注塑成哑铃状的样条，模具温度为25-40℃。然后在1mm/min的速率进行拉伸测试，测得其断裂伸长率为830％，弹性模量为430MPa。Weigh 41 parts of dried PP, 30 parts of PE, 29 parts of PET, and take 4 parts of the compatibilizer prepared in Example 8, stir them uniformly by physical, and then add them into a twin-screw extruder for melt blending. The blend was blended at 255-260 °C for 5 min at a speed of 10-20 rpm. Subsequently, it is injection molded into dumbbell-shaped splines at 250-255° C., and the mold temperature is 25-40° C. Then a tensile test was carried out at a speed of 1 mm/min, and the measured elongation at break was 830%, and the modulus of elasticity was 430 MPa.
对比例1Comparative example 1
称取干燥好的PP 41份，PE 30份，PET 29份，将其通过物理搅拌均匀，然后加入双螺杆挤出机中进行熔融共混。共混物在255-260℃下以10-20rpm的速度共混5min。随后在250-255℃下注塑成哑铃状的样条，模具温度为25-40℃。然后在1mm/min的速率进行拉伸测试，测得其断裂伸长率为9％，弹性模量为232MPa。Weigh 41 parts of dried PP, 30 parts of PE, and 29 parts of PET, stir them evenly by physical stirring, and then put them into a twin-screw extruder for melt blending. The blend was blended at 255-260 °C for 5 min at a speed of 10-20 rpm. Subsequently, it is injection molded into dumbbell-shaped splines at 250-255° C., and the mold temperature is 25-40° C. Then a tensile test was carried out at a speed of 1 mm/min, and the measured elongation at break was 9%, and the modulus of elasticity was 232 MPa.
对比例2Comparative example 2
称取干燥好的PP 41份，PE 30份，PET 29份，取PP-PE二嵌段共聚物4份作为增容剂，将其通过物理搅拌均匀，然后加入双螺杆挤出机中进行熔融共混。共混物在255-260℃下以10-20rpm的速度共混5min。随后在250-255℃下注塑成哑铃状的样条，模具温度为25-40℃。然后在1mm/min的速率进行拉伸测试，测得其断裂伸长率为61％，弹性模量为401MPa。Weigh 41 parts of dry PP, 30 parts of PE, 29 parts of PET, take 4 parts of PP-PE diblock copolymer as compatibilizer, stir it evenly by physical, and then put it into the twin-screw extruder for melting Blend. The blend was blended at 255-260 °C for 5 min at a speed of 10-20 rpm. Subsequently, it is injection molded into dumbbell-shaped splines at 250-255° C., and the mold temperature is 25-40° C. Then a tensile test was carried out at a speed of 1mm/min, and the measured elongation at break was 61%, and the modulus of elasticity was 401MPa.
表1各试验例和对比例的原料比及性能比较Raw material ratio and performance comparison of each test example and comparative example in table 1
由对比例和具体实施例可以看出，本发明的增容剂可以有效提高聚烯烃与极性聚酯之间的相容性，为生物可降解塑料的制备和大规模废旧塑料回收处理提供了一个有效的解决方案。It can be seen from the comparative examples and specific examples that the compatibilizer of the present invention can effectively improve the compatibility between polyolefins and polar polyesters, and provide a good solution for the preparation of biodegradable plastics and large-scale recycling of waste plastics. A working solution.
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection of the present invention. within range.
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| CN202310691954.0ACN116535656B (en) | 2023-06-12 | 2023-06-12 | A graft copolymer and its preparation method and application |
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| CN202310691954.0ACN116535656B (en) | 2023-06-12 | 2023-06-12 | A graft copolymer and its preparation method and application |
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| CN202310691954.0AActiveCN116535656B (en) | 2023-06-12 | 2023-06-12 | A graft copolymer and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3485777A (en)* | 1966-03-28 | 1969-12-23 | Us Plywood Champ Papers Inc | Compatibilization of polymers by adding graft copolymers |
| JPH0381333A (en)* | 1989-08-24 | 1991-04-05 | Tonen Corp | Method for producing polyolefin-polyester graft copolymer |
| CN101671420A (en)* | 2009-09-17 | 2010-03-17 | 中国科学技术大学 | PET alloy material, special compatibilizer thereof and preparation method thereof |
| CN104419008A (en)* | 2013-08-30 | 2015-03-18 | 北京化工大学 | Method for grafting polymer chain employing biomass polysaccharide |
| US20220195127A1 (en)* | 2019-04-01 | 2022-06-23 | Regents Of The University Of Minnesota | Multiblock Copolymers of Polyolefins and Polyesters |
| CN115703854A (en)* | 2021-08-09 | 2023-02-17 | 复旦大学 | Compatibilizer and application thereof in preparation of polyolefin/polysaccharide polymer composite material |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3485777A (en)* | 1966-03-28 | 1969-12-23 | Us Plywood Champ Papers Inc | Compatibilization of polymers by adding graft copolymers |
| JPH0381333A (en)* | 1989-08-24 | 1991-04-05 | Tonen Corp | Method for producing polyolefin-polyester graft copolymer |
| CN101671420A (en)* | 2009-09-17 | 2010-03-17 | 中国科学技术大学 | PET alloy material, special compatibilizer thereof and preparation method thereof |
| CN104419008A (en)* | 2013-08-30 | 2015-03-18 | 北京化工大学 | Method for grafting polymer chain employing biomass polysaccharide |
| US20220195127A1 (en)* | 2019-04-01 | 2022-06-23 | Regents Of The University Of Minnesota | Multiblock Copolymers of Polyolefins and Polyesters |
| CN115703854A (en)* | 2021-08-09 | 2023-02-17 | 复旦大学 | Compatibilizer and application thereof in preparation of polyolefin/polysaccharide polymer composite material |
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| CN116535656B (en) | 2025-04-04 |
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