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Easy cross-linking biodegradable resin and preparation method thereof

A technology for biodegradable resins and mixtures, applied in the field of readily cross-linkable biodegradable resins and their preparation, can solve the problem of failing to impart functionalization to the PGA main chain structure, failing to improve compatibility and processing adaptability, and having no high reactivity functional groups and other problems, to achieve the effect of good biodegradability, high crystallinity and high melting point characteristics

Active Publication Date: 2022-01-18
JIANGSU JINJU ALLOY MATERIAL
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although this solution can improve the hydrolysis resistance of PGA, it does not give the functionalization of the main chain structure of PGA, and cannot improve the compatibility and processing adaptability of PGA when it is blended with other types of polymers.
[0010] The patent with the publication number CN 102718955 A reports a method for preparing copolyesters by copolymerizing glycolic acid and its esters with terephthalic acid and ethylene glycol. The method is to prepare copolyesters by random copolymerization, and the method prepares The copolyester has only certain degradability, theoretically it is not a real biodegradable resin
Furthermore, the copolyester also does not have highly reactive functional groups due to the comonomer

Method used

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  • Easy cross-linking biodegradable resin and preparation method thereof
  • Easy cross-linking biodegradable resin and preparation method thereof
  • Easy cross-linking biodegradable resin and preparation method thereof

Examples

Experimental program
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preparation example Construction

[0048]

[0049] The easy-to-crosslink biodegradable resin is prepared by combining polyglycolic acid and polyethylene butenediolate under the action of a catalyst through melt transesterification and solid-state reaction, specifically:

[0050] The preparation method of easy crosslinking biodegradable resin, it comprises the steps:

[0051] (1) Mix polyglycolic acid and polyethylene butylene dioate in the reaction kettle according to the mass ratio (1-19): 1 to obtain a mixture, add catalyst and stabilizer to the mixture and stir it under vacuum condition , feed nitrogen to press out the obtained resin mixture, and crush to obtain resin particles;

[0052] (2) Put the resin particles into a vacuum drum for solid-phase reaction, cool and discharge with nitrogen gas, and obtain an easily crosslinkable biodegradable resin.

[0053] In fact, the stabilizer may be 4,4'-thiobis(6-tert-butyl-3-methylphenol). Because PGA is different from ordinary polymers, its thermal stability i...

Embodiment 1

[0074] The preparation method of the easy crosslinking biodegradable resin of the present embodiment comprises the steps:

[0075] (1) Preparation of polyglycolic acid (PGA): Take 10mol glycolide and open the ring at 180°C under the action of 0.001mol (that is, the amount is 1 / 10000 of the molar amount of glycolide) stannous octoate (as a catalyst) Obtained by polymerization, the weight average molecular weight of PGA measured by GPC is 6.54×10 4 g / mol, and molecular weight distribution width M W / M n is 1.46;

[0076] (2) Preparation of polyethylene maleate: get 500g maleic acid, 100g maleic anhydride and 900g ethylene glycol in 7.5g (that is, the amount is the total mass of the monomers thrown) 0.5% of tetrabutyl titanate (as a catalyst), after high-pressure esterification, it is obtained by reduced-pressure polymerization; the number-average molecular weight of polyethylene butenedioate is 1.22×10 4 g / mol, and molecular weight distribution width M W / M n is 2.04;

[...

Embodiment 2

[0080] The preparation method of the easy crosslinking biodegradable resin of the present embodiment comprises the steps:

[0081] (1) Preparation of polyglycolic acid (PGA): 10 mol of glycolide is subjected to ring-opening polymerization at 180° C. , the weight-average molecular weight of PGA measured by GPC was 6.54×10 4 g / mol, and molecular weight distribution width M W / M n is 1.46;

[0082] (2) Preparation of polyethylene maleate: take 600g maleic acid and 900g ethylene glycol in tetrabutyl titanate (as a catalyst) (the amount is 0.5% of the total mass of the monomers thrown) %) under the action of high-pressure esterification and compression polymerization under reduced pressure; 4 g / mol, and molecular weight distribution width M W / M n is 2.32;

[0083] (3) 160g polyglycolic acid and 40g polyethylene glycol ester are mixed in reactor to obtain mixture, add 0.1wt% transesterification catalyst in mixture (the mol ratio of bismuth isooctanoate and zinc acetate is 2 ...

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Abstract

The invention provides an easily cross-linked biodegradable resin and a preparation method thereof. The method is as follows: firstly, polyglycolic acid is obtained by ring-opening polymerization of glycolide; then, unsaturated aliphatic diacid or unsaturated aliphatic diacid anhydride polycondensation with ethylene glycol to obtain polyunsaturated fatty acid ethylene glycol ester; finally, polyglycolic acid and polyunsaturated fatty acid ethylene glycol ester are prepared by melt mixing and solid-state reaction under the conditions of transesterification catalyst and stabilizer Yes; the present invention adopts the "block solid-phase transesterification" technology, and the transesterification reaction mainly occurs in the amorphous region of the polyglycolic acid component, while the transesterification reaction hardly occurs in the crystalline region, thereby minimizing the ester exchange reaction. The effect of the exchange reaction on the polyglycolic acid crystal region, so that the prepared easy-to-crosslink biodegradable resin has the advantages of good degradation performance, good crystallization performance and good heat resistance; The bond structure makes the prepared resin have the characteristics of easy cross-linking.

Description

technical field [0001] The invention belongs to the technical field of degradable plastics, and in particular relates to an easily cross-linked biodegradable resin and a preparation method thereof. Background technique [0002] Synthetic resins and plastics have been favored by people for their convenient processing properties since their birth. However, the widespread use of conventional non-degradable plastic products and the inconvenient recycling have also brought serious environmental problems. Therefore, biodegradable plastics are attracting more and more attention. [0003] Polyglycolic acid (PGA) is a biodegradable resin with excellent degradation properties, high barrier properties and high mechanical properties, but due to its low glass transition temperature (Tg) Hydrolytic degradation reactions are prone to occur at room temperature with a certain humidity, which seriously affects the preservation of PGA products. It should be pointed out that in fact, the hyd...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G81/00
Inventor 翁伟明吴维果贡秀君刘志刚孙朝晖
Owner JIANGSU JINJU ALLOY MATERIAL