CN100489009C - Degradable unsaturated carbamide resin of polyester amide, and synthetic method - Google Patents

Abstract

A degradable unsaturated polyester-amidourea resin used for disposable food container, packing material, plastic bag, medicinal coating, capsule and slow-releasing material, etc is prepared from C2-C4 binary alcohol, anti-butenedioic acid or maleic anhydride, and urea through fusing and polycondensating. It can be modified by starch or calcium carbonate powder.

Description

Degradable unsaturated carbamide resin of polyester amide and synthetic method thereof

Technical field

The present invention relates to the macromolecular material and the method for chemosynthesis environmentally degradable.Adopt unsaturated diacid (acid anhydride) (MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE) and C₂～C₄Aliphatic dihydric alcohol or Diethylene Glycol, urea copolymerization make the unsaturated polyester amide urea matrix resin of environmentally degradable.Wherein unsaturated diacid (acid anhydride) (MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE) can be partly by a kind of replacement in hexanodioic acid, phthalic anhydride, the m-phthalic acid.This resinoid available starches and Paris white are done weighting agent, make starch and Paris white and fill unsaturated carbamide resin of polyester amide.This resinoid and filling-modified resin thereof can be used as preparation disposable tableware, wrapping material, shopping bag, flowerpot, medical science articles for use, drug coating or capsule, medicine delays the material that (control) releases material, agricultural mulching etc.This resinoid reclaims the slow release fertilizer that can be used as paddy field, dry crop with the back.Advantages such as this resinoid is nontoxic in addition, cost is lower.

Technical background

The white pollution that adopts the disposable product of non-degraded macromolecular material preparation such as foam food boxes, plastic cup, plastics bag etc. to cause has arrived stage beyond forbearance.China abandons 4,000,000 tons non-degraded disposable product every year approximately, causes the serious wasting of resources and environmental disruption.Adopt degradable high polymer material to prepare disposable product and can satisfy environmental requirement, thereby come into one's own, tempo is very fast, (Zhou Peng such as disposable tableware, wrapping material, shopping bag, flowerpot, medical science articles for use, agricultural mulching now have been widely used in, Tan Yingjie, Liang Yurong, progress in Study of Degradable Plastics.The Shanxi chemical industry, 2005,25 (1): 23-27).The material that uses comprises photodegradable plastics (as ethene one CO multipolymer and ethene one ketene copolymer) and biodegradable plastic (as poly(lactic acid), polycaprolactone, poly-succsinic acid fourth diester, starch etc.).Wherein with starch base environment degradable high polymer material consumption maximum (Wang Yunfang, Wang Rumin, Zhao Jin, Guo Zengchang, starch base environment degradable high polymer material progress.The material Leader, 2005,19 (4): 12-16).Niu Liming etc. point out that most existing degradable plastics tableware adds starch by thermoplastics and photodegradable aid is made, can only make plastic tableware be cracked into the fritter fragment behind the starch degradation, can not further degrade, reclaim difficulty, still can cause potential to pollute soil.(Yang Xin is refined for Niu Liming, Fu Xiangkai, the development of disposable degradable environment protecting tableware.Southwestern Normal University's journal, 2005,03-04:91-04).Other existing degradable high polymer material or because of cost is too high, or because of can not degrading fully, or because of poor-performing, or because of the mass consumption forest reserves, or, preparation process make its application be restricted (Song Zhaozheng, Zhao Mifu, production Technique of Degradable Plastic because of easily polluting.The Speciality Petrochemicals progress, 2005,6 (3): 13-20).And existing degradable high polymer material only is satisfied with in environment mostly and is rotted, and utilization ratio is low again for it.Developing novel degradable macromolecular material excellent combination property, recyclable utilization, lower-cost comes into one's own.

Summary of the invention

The technical problem to be solved in the present invention is, defective at the prior art existence, a kind of unsaturated carbamide resin of polyester amide and synthetic method thereof of environmentally degradable are proposed, with its can synthesize obtain degradation rate adjustable, nontoxic, with after can make slow release fertilizer, lower-cost unsaturated carbamide resin of polyester amide, it can be widely used as the matrix resin that disposable tableware, wrapping material, shopping bag, refuse bag, flowerpot, medical science articles for use, drug coating or capsule, medicine slow (control) are released material, agricultural mulching etc.This resinoid rich in starch and nitrogen element reclaim the slow release fertilizer that can be used as paddy field, dry crop with the back.As be used for the saltings, also can play the effect that reduces soil alkalescence.Owing to be utilization of waste material, can partly solve at least existing slow release fertilizer price more expensive,

Be applicable to the problems such as slow release fertilizer shortcoming in southern paddy field.

One of technical solution of the present invention is that the general structure of the unsaturated carbamide resin of polyester amide of described environmentally degradable is:

M is MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE-C in the formula₂～C₄The mole number of the chain link of aliphatic dihydric alcohol or Diethylene Glycol polyester, n are the mole number of the chain link of MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE-urea polyester amide urea, m/n=1/5～5/1; MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE can be partly by a kind of replacements in hexanodioic acid, phthalic anhydride, the m-phthalic acid.

Two of technical solution of the present invention is that the step of the synthetic method of the unsaturated carbamide resin of polyester amide of described environmentally degradable is:

(1) with MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE, C₂～C₄Aliphatic dihydric alcohol or Diethylene Glycol mix by certain mol proportion with urea, pack into and be with in the container of water trap, place silicone oil bath, nitrogen protection, electronic stirring, the reacting by heating certain hour distillates by product moisture, synthetic obtain yellowish to dark-brown thickness liquid state or the transparent unsaturated polyester amide urea of semi-solid state;

(2) polymerization finishes, and is cooled to 120～150 ℃, adds a certain amount of starch or Paris white, fully stirs, and pours out while hot, is cooled to room temperature (25 ℃) and obtains flaxen starch filled unsaturated carbamide resin of polyester amide.

In the synthetic method of the present invention, described MALEIC ANHYDRIDE ofstep 1 or FUMARIC ACID TECH GRADE: C₂～C₄Aliphatic dihydric alcohol or Diethylene Glycol: the mol ratio of urea is 2:1.8～1.0:0.2～1.0; Described temperature of reaction is 100～200 ℃, and the reaction times is 30～300 minutes; Described MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE can be partly by a kind of replacements in hexanodioic acid, phthalic anhydride, the m-phthalic acid, and MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE account for more than 50% of diacid (acid anhydride) total mole number.The starch of the described adding of step 2 or the total mass number of Paris white are 30～60% of system total mass number.

The curing of the unsaturated carbamide resin of polyester amide that unsaturated carbamide resin of polyester amide or starch and Paris white are filled is, use initiator to make unsaturated carbamide resin of polyester amide crosslinked down at 80 ℃-130 ℃, or heating made resin crosslinks in 5-30 minute under 180 ℃-230 ℃, and molecular weight increases and solidifies.Employed initiator is a kind of in dibenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, the isopropyl benzene hydroperoxide.

Below the present invention made further specify.

Based on the preparation degradable resin should minimize cost, novel, nontoxic, excellent combination property, recycling consideration, cheap raw materials such as employing urea, starch, Paris white have been designed, and inexpensive raw materials such as MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE, phthalic anhydride, m-phthalic acid, hexanodioic acid, ethylene glycol or other common glycol, select relatively mild reaction conditions, synthetic prepared degradation rate adjustable, nontoxic, with after can make slow release fertilizer, lower-cost unsaturated carbamide resin of polyester amide, the general structure of this resinoid is:

This resinoid can be widely used as disposable tableware, wrapping material, shopping bag, refuse bag, flowerpot, medical science articles for use, capsule for medicine, medicine slow (control) and release the matrix resin of material, agricultural mulching etc., so very high using value is arranged.Such material has not yet to see report.

The sign of synthetic unsaturated carbamide resin of polyester amide:

The synthetic unsaturated carbamide resin of polyester amide all characterizes with FT-IR, and such FT-IR spectrogram is comparatively complicated, demonstrates the charateristic avsorption band of different monomers residue functionalgroup.Accompanying drawing 1 is the IR spectrogram (mol ratio: urea/MALEIC ANHYDRIDE/ethylene glycol=1.0/4.01/3.1) of unsaturated carbamide resin of polyester amide.Among the figure mainly at 1718cm^-1The C=O stretching vibration charateristic avsorption band that strong polyester is arranged is at 1647cm^-1Unsaturated polyester C=C stretching vibration charateristic avsorption band is arranged, and undersaturated C=C key can participate in cross-linking and curing reaction.At 2987cm^-1C-H stretching vibration absorption peak is arranged.At 3236-3452cm^-1Wide-COOH the absorption peak at place shows that residual-COOH is arranged in the polymkeric substance, can participate in the curing reaction that molecular weight increases.Experimental result shows the structure and theoretical expect consistent of all synthetic polymers.

Unsaturated carbamide resin of polyester amide performance of the present invention:

1) curing performance

The unsaturated carbamide resin of polyester amide oligopolymer is better mobile when being higher than 100 ℃, and processing characteristics is good, is easy to mix with fillers such as starch, Paris whites.Be rich in undersaturated C=C key in this resinoid, use down a kind of in dibenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, the isopropyl benzene hydroperoxide unsaturated link(age) in the unsaturated carbamide resin of polyester amide is reacted to each other and crosslinked at 80 ℃-130 ℃ as initiator, or heating made resin crosslinks in 5-30 minute under 180 ℃-230 ℃, molecular weight increases, be cooled to 120 ℃ of after fixing hardening, become strong and tough material.

2) degradation property

Adopt hot melt process, prepare cylindrical unsaturated polyester amide urea rod (φ 4mm, long 10mm) with homemade tetrafluoroethylene mould, excellent quality is about 150mg.The unsaturated polyester amide urea rod is placed the distilled water of 100mL, and (25 ℃) leave standstill and carry out degradation experiment under the room temperature.Take out sample at regular intervals,, put into P with distillation washing sample surfaces₂O₅Dry 24h weighs in the vacuum drier, by calculating degradation rate of poor quality before and after the sample degraded.Experimental result shows, in the distilled water, and the time of gained unsaturated polyester amideurea material degradation 80%, different with forming, do not wait from 1 month to 1 year time.In distilled water, unsaturated polyester amide urea material degradation speed is influenced greatly by urea content.Urea content is higher, and degradation rate is faster.Unsaturated polyester amide urea material degradation speed belongs to pH according to patience, and degradation rate is slow in acid solution, and degradation rate is fast in alkaline solution.Proof stick (long 5mm asembodiment 1 synthetic unsaturated carbamide resin of polyester amide, diameter 4mm) be that complete degradation time is 53 ± 6 minutes in 11 the alkaline solution under 25 ℃ in the pH value, in the pH value is that complete degradation time is 107 ± 13 days in 7 the water, is that complete degradation time is 119 ± 15 days in 3 the acid solution in the pH value.Consider the adjustability of material degradation speed; such material is except the degradation material that can be used as disposable product; also be expected to as medicine dressing or capsule; can protect medicine not to be subjected to stomach acids destroy under one's belt and do not allow stomach by medicine irritation; and in the small intestine of alkaline environment; can in time degrade as medicine dressing or capsular material, discharge parcel medicine wherein, make it to be absorbed smoothly by small intestine.The mechanical property that material is good can withstand the destruction of gastrointestinal peristalsis when guaranteeing it as medicine dressing or capsule, make medicine arrive small intestine smoothly.

3) mechanical property

The synthetic unsaturated carbamide resin of polyester amide is rich in polar ester bond and acid amides-urea key, gives material good mechanical property.The mechanical property of material is influenced greatly by condition of cure also.Solidification value height, set time are long, and then the material degree of crosslinking is big, and is very strong, but toughness is relatively poor; Solidification value is lower, set time is shorter, and then the material degree of crosslinking is little, good toughness, but soft, hardness is not enough.So select suitable condition of cure, to obtain comprehensive mechanical property material preferably.Use initiator to cause when solidifying temperature and get 80 ℃-130 ℃ and be advisable, get heat-up time and be advisable in 5-30 minute.Use dibenzoyl peroxide to make initiator during 80 ℃ of curing, use a kind of initiator of doing in di-t-butyl peroxide, dicumyl peroxide, the isopropyl benzene hydroperoxide during 110 ℃-130 ℃ curing.Heat curing temperature is got 180 ℃-230 ℃ and is advisable, and gets heat-up time and is advisable in 5-30 minute.Test print asembodiment 1 synthetic unsaturated carbamide resin of polyester amide heats 20 minutes crosslinking curings down at 200 ℃, and the yield strength that records is 11.3657MPa, and breaking tenacity is 10.9901MPa.

4) resistance toheat

The resistance toheat (accompanying drawing 2) that adopts DSC and TG thermal analysis system to test unsaturated carbamide resin of polyester amide.Record behind the synthetic unsaturated polyester amide urea crosslinking curing low at thermal weight loss below 130 ℃, quite stable, resistance toheat is better, satisfies practical requirement.

As known from the above, the present invention is the unsaturated carbamide resin of polyester amide and the synthetic method thereof of environmentally degradable, can synthesize with it and to obtain adjustable, nontoxic, the lower-cost unsaturated carbamide resin of polyester amide of degradation rate, it can be widely used as the matrix resin that disposable tableware, wrapping material, shopping bag, refuse bag, flowerpot, medical science articles for use, drug coating or capsule, medicine slow (control) are released material, agricultural mulching etc.This resinoid rich in starch and nitrogen element reclaim the slow release fertilizer that can be used as paddy field, dry crop with the back.

Description of drawings

Fig. 1 is the IR spectrogram (mol ratio: urea/MALEIC ANHYDRIDE/ethylene glycol=1.0/4.0/3.1) of unsaturated carbamide resin of polyester amide;

Fig. 2 is hot analysis of spectra (DSC and TG, the mol ratio: urea/MALEIC ANHYDRIDE/ethylene glycol=1.0/4.0/3.1) of unsaturated carbamide resin of polyester amide.

Embodiment

Embodiment 1: unsaturated carbamide resin of polyester amide synthetic:

19.60g MALEIC ANHYDRIDE (0.20 mole), 3.00g urea (0.05 mole) and 9.92g ethylene glycol (0.16 mole) are mixed, pack in the 250ml there-necked flask of being with water trap, place silicone oil bath, electronic stirring, 100 ℃ were reacted 20 minutes down.Be warming up to 150 ℃, melt polymerization is 40 minutes in the nitrogen atmosphere, is warming up to 180 ℃ again, and melt polymerization is 120 minutes in the nitrogen atmosphere, is warming up to 200 ℃ again, melt polymerization in the nitrogen atmosphere.Treat that the distilled reaction water reaches 80% o'clock of theoretical amount, stop polymerization, be cooled to 150 ℃ and pour out, obtain the transparent solid unsaturated carbamide resin of polyester amide of dark-brown after the cooling.

Embodiment 2: starch filled unsaturated carbamide resin of polyester amide synthetic:

23.20g FUMARIC ACID TECH GRADE (0.20 mole), 3.00g urea (0.05 mole) and 16.96g one condensed ethandiol (0.16 mole) are mixed, pack in the 250ml there-necked flask of being with water trap, place silicone oil bath, electronic stirring, 100 ℃ were reacted 20 minutes down.Be warming up to 150 ℃, melt polymerization is 40 minutes in the nitrogen atmosphere, is warming up to 180 ℃ again, and melt polymerization is 120 minutes in the nitrogen atmosphere, is warming up to 200 ℃ again, and melt polymerization is 15 minutes in the nitrogen atmosphere.Treat that the distilled reaction water reaches 80% o'clock of theoretical amount, add the starch that accounts for reaction systemtotal mass 50%, fully stir, be cooled to 150 ℃ and pour out, obtain the starch filled unsaturated carbamide resin of polyester amide of opaque faint yellow solid shape after the cooling.

Claims (6)

1, a kind of unsaturated carbamide resin of polyester amide of environmentally degradable is characterized in that, its general structure is:

M is MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE-C in the formula₂～C₄The mole number of the chain link of aliphatic dihydric alcohol or Diethylene Glycol polyester, n are the mole number of the chain link of MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE-urea polyester amide urea, m/n=1/5～5/1; MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE can be partly by a kind of replacements in hexanodioic acid, phthalic anhydride, the m-phthalic acid.

2, the unsaturated carbamide resin of polyester amide of environmentally degradable according to claim 1, it is characterized in that, such unsaturated carbamide resin of polyester amide can directly use, and also available starches or Paris white are filled, and obtains starch or Paris white and fills unsaturated carbamide resin of polyester amide.

3, a kind of synthetic method of unsaturated carbamide resin of polyester amide of environmentally degradable is characterized in that, steps of the method are:

(1) with MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE, C₂～C₄Aliphatic dihydric alcohol or Diethylene Glycol mix by certain mol proportion with urea, pack into and be with in the container of water trap, place silicone oil bath, nitrogen protection, electronic stirring, the reacting by heating certain hour distillates by product moisture, synthetic obtain yellowish to dark-brown thickness liquid state or the transparent unsaturated polyester amide urea of semi-solid state;

(2) polymerization finishes, and is cooled to 120～150 ℃, adds a certain amount of starch or Paris white, fully stirs, and pours out while hot, is cooled to room temperature (25 ℃) and obtains flaxen starch or Paris white filling unsaturated carbamide resin of polyester amide.

4, according to the synthetic method of the unsaturated carbamide resin of polyester amide of the described environmentally degradable of claim 3, it is characterized in that described MALEIC ANHYDRIDE of step 1 or FUMARIC ACID TECH GRADE: C₂～C₄Aliphatic dihydric alcohol or Diethylene Glycol: the mol ratio of urea is 2:1.8～1.0:0.2～1.0; Described temperature of reaction is 100～200 ℃, and the reaction times is 30～300 minutes; Described MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE can be partly by a kind of replacements in hexanodioic acid, phthalic anhydride, the m-phthalic acid, and MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE account for more than 50% of diacid (acid anhydride) total mole number.

5, according to the synthetic method of the unsaturated carbamide resin of polyester amide of the described environmentally degradable of claim 3, it is characterized in that the starch of the described adding of step 2 or the total mass number of Paris white are 30～60% of system total mass number.

6, according to the synthetic method of the unsaturated carbamide resin of polyester amide of the described environmentally degradable of claim 3, it is characterized in that, the curing of the unsaturated carbamide resin of polyester amide that unsaturated carbamide resin of polyester amide or starch and Paris white are filled is to use initiator to make unsaturated carbamide resin of polyester amide crosslinked down at 80 ℃-130 ℃, or heating made resin crosslinks in 5-30 minute under 180 ℃-230 ℃, and molecular weight increases and solidifies; Employed initiator is a kind of in dibenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, the isopropyl benzene hydroperoxide.

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