CN119192553A - A high melt strength polyglycolide material and preparation method thereof - Google Patents
A high melt strength polyglycolide material and preparation method thereof Download PDFInfo
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- CN119192553A CN119192553A CN202411465432.XA CN202411465432A CN119192553A CN 119192553 A CN119192553 A CN 119192553A CN 202411465432 A CN202411465432 A CN 202411465432A CN 119192553 A CN119192553 A CN 119192553A
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- 229920000954 Polyglycolide Polymers 0.000 title claims abstract description 91
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 34
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 31
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 31
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 31
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical group OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims abstract description 29
- 239000000155 melt Substances 0.000 claims abstract description 28
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 24
- 238000001125 extrusion Methods 0.000 claims abstract description 23
- 150000002978 peroxides Chemical class 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000012271 agricultural production Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000004806 packaging method and process Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 18
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 claims 1
- 125000003700 epoxy group Chemical group 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 150000003254 radicals Chemical class 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000007348 radical reaction Methods 0.000 abstract description 3
- 238000007142 ring opening reaction Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- -1 t-butylperoxy Chemical group 0.000 description 3
- DEKVAWHRMRNKMI-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3-propan-2-ylbenzene Chemical group CC(C)C1=CC=CC(OOC(C)(C)C)=C1OOC(C)(C)C DEKVAWHRMRNKMI-UHFFFAOYSA-N 0.000 description 2
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AZWATAMGZFKYHZ-UHFFFAOYSA-N 2-(chloroamino)butanoic acid Chemical compound CCC(NCl)C(O)=O AZWATAMGZFKYHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000000520 microinjection Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
本发明公开了一种高熔体强度聚乙交酯材料及其制备方法，属于高分子材料加工改性技术领域。所述高熔体强度聚乙交酯材料的原料包括：聚乙交酯100份、助剂0.1～10份、引发剂0.01～3份；所述助剂为腰果酚缩水甘油醚；制备方法包括以下步骤：将聚乙交酯、助剂和引发剂混合均匀得到混合物料，将所述混合物料熔融挤出，得到所述高熔体强度聚乙交酯材料。熔融挤出过程中，在过氧化物类引发剂作用下，助剂的双键与聚乙交酯分子的仲碳进行自由基反应，然后环氧基和聚乙交酯分子端羟基或端羧基进行开环反应，得到高熔体强度接枝聚乙交酯材料。本发明的制备方法简单，制得的高熔体强度聚乙交酯材料可用于农业生产、食品包装及生物医学等领域。
The invention discloses a high melt strength polyglycolide material and a preparation method thereof, and belongs to the technical field of polymer material processing and modification. The raw materials of the high melt strength polyglycolide material include: 100 parts of polyglycolide, 0.1-10 parts of auxiliary agent, and 0.01-3 parts of initiator; the auxiliary agent is cardanol glycidyl ether; the preparation method includes the following steps: polyglycolide, auxiliary agent and initiator are uniformly mixed to obtain a mixed material, and the mixed material is melt-extruded to obtain the high melt strength polyglycolide material. During the melt extrusion process, under the action of a peroxide initiator, the double bond of the auxiliary agent reacts with the secondary carbon of the polyglycolide molecule by free radical reaction, and then the epoxy group and the terminal hydroxyl group or terminal carboxyl group of the polyglycolide molecule undergo a ring-opening reaction to obtain a high melt strength grafted polyglycolide material. The preparation method of the invention is simple, and the obtained high melt strength polyglycolide material can be used in agricultural production, food packaging, biomedicine and other fields.
Description
Technical Field
The invention relates to the technical field of processing and modification of high polymer materials, in particular to a high melt strength polyglycolide material and a preparation method thereof.
Background
Polyglycolide (PGA), a simple linear aliphatic polyester, is a world-accepted material that protects the earth's environment and life, and has excellent degradability and excellent force-blocking properties. Because of its good biocompatibility, PGA has been widely used in medical absorbable surgical suture lines, biodegradable polymer stents, drug release-controlled and human tissue-simulating products, etc. However, PGA has been severely limited in its application in the related art due to the disadvantages of excessively high melt flow rate, excessively low melt strength, etc. of PGA at processing temperatures.
Increasing the melt strength of PGA may be achieved by increasing the relative molecular weight, chain extension or crosslinking. Wherein the construction of the crosslinked structure is generally by reactive extrusion. The principle is that an initiator is utilized to initiate an auxiliary agent in an internal mixer to generate small molecular free radicals, the free radicals react with secondary hydrocarbon of a PGA molecular chain to form macromolecular free radicals, and branching or crosslinking reaction is carried out under the participation of the auxiliary agent, so that the melt strength of the PGA is improved.
Most of the commonly used assistants are petroleum-based assistants, but environmental pollution is avoided. Moreover, the properties of the obtained PGA material are not very good and still remain to be improved. Therefore, there is a need to develop a bio-based aid to replace the conventional petroleum-based aid, and to obtain a PGA material with better properties while reducing the dependence on petroleum resources.
Disclosure of Invention
The invention aims to provide a high-melt-strength polyglycolide material and a preparation method thereof, so as to solve the problems in the prior art. The high-melt-strength polyglycolide material has excellent performance and is suitable for the fields of agricultural production, food packaging, biomedicine and the like.
In order to achieve the above object, the present invention provides the following solutions:
According to one of the technical schemes, the high-melt-strength polyglycolide material (actually cardanol glycidyl ether grafted polyglycolide) comprises the following raw materials in parts by mass:
100 parts of polyglycolide, 0.1-10 parts of auxiliary agent and 0.01-3 parts of initiator;
the auxiliary agent is cardanol glycidyl Ether (ECA);
The structural formula of the cardanol glycidyl ether is Where n=0, 2, 4 or 6.
Further, the melt index of the polyglycolide is 5-25 g/10min.
Further, the initiator is a peroxide initiator.
Further, the peroxide initiator is bis-tert-butylperoxyisopropyl benzene, dicumyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, dibenzoyl peroxide or 1, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane.
Further, the saidIn (a):
when n=0, -C 15H31-n has the formula
When n=2, -C 15H31-n has the formula
When n=4, -C 15H31-n has the formula
When n=6, -C 15H31-n has the formula
Further, the cardanol glycidyl ether comprises the following components in percentage by weight:
n=0 0-10%, And is not 0;
n=2 0-54%, And is not 0;
n=4 0-43%, And is not 0;
n=6 0 To 61%, and not 0.
The second technical scheme of the invention is that the preparation method of the high-melt-strength polyglycolide material comprises the following steps of uniformly mixing the polyglycolide, an auxiliary agent and an initiator to obtain a mixed material, and carrying out melt extrusion on the mixed material to obtain the high-melt-strength polyglycolide material.
In the melt extrusion process, under the action of a peroxide initiator, the double bond of the auxiliary agent and secondary carbon of the polyglycolide molecule undergo a free radical reaction, and then epoxy groups and hydroxyl or carboxyl ends of the polyglycolide molecule undergo a ring opening reaction, so that the high melt strength grafted polyglycolide material is obtained. The reaction equation in the reaction system is as follows:
when n=0, the reaction equation is:
when n=2, the reaction equation is:
when n=4, the reaction equation is:
when n=6, the reaction equation is:
Wherein the structural formula of O-R-O is as follows:
(when the peroxide initiator is di-t-butylperoxyisopropyl benzene);
(when the peroxide initiator is dicumyl peroxide);
(when the peroxide initiator is 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane);
(when the peroxide initiator is 1, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane);
Or (b) (When the peroxide initiator is dibenzoyl peroxide).
Further, the mixing is performed in a high speed mixer.
Further, the rotational speed of the mixing is 500-2000 rpm, and the time is 5-15min.
Further, the melt extrusion is performed in an internal mixer or a twin screw extruder.
Further, the temperature of the melt extrusion is 230-260 ℃, the rotating speed is 90-200 rpm, and the time is 1-5 min.
The third technical scheme of the invention is that the high melt strength polyglycolide material is applied to the fields of agricultural production, food packaging or biomedicine.
The invention discloses the following technical effects:
The auxiliary agent used in the invention is cardanol glycidyl ether which has unsaturated double bond and epoxy group, the unsaturated double bond can be initiated by peroxide to generate free radical reaction under high temperature condition, and the epoxy group is easy to generate ring opening reaction with functional groups such as hydroxyl end group or carboxyl end group of polyglycolide. The cardanol glycidyl ether containing the epoxy group is obtained by substituting the phenolic hydroxyl group of cardanol with the epoxy group, and has the characteristics of low cost, good reproducibility and rich sources.
According to the invention, the poly glycolide and the auxiliary agent (cardanol glycidyl ether) are used as main raw materials, under the action of the peroxide initiator, the double bond on the auxiliary agent is bonded with the secondary carbon of the poly glycolide molecule, and then the epoxy group and the hydroxyl or carboxyl at the end of the poly glycolide molecule undergo a chain extension reaction, so that the branching degree of the poly glycolide can be effectively improved, the prepared bio-based grafted poly glycolide material has the characteristic of high melt strength, and the preparation method is simple, thereby meeting the requirements of the fields of agricultural production, food packaging, biomedicine and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the complex viscosity as a function of frequency for the grafted PGA of examples 1-2 and comparative examples 1-2, as well as for pure PGA, in a dynamic rheology test;
FIG. 2 is a Cole-Cole plot of the grafted PGA of examples 1-2 and comparative examples 1-2, as well as pure PGA;
FIG. 3 is a graph showing relaxation time spectra of the grafted PGA of examples 1-2 and comparative examples 1-2 and pure PGA.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The invention provides a high-melt-strength polyglycolide material, which comprises the following raw materials in parts by weight:
100 parts of polyglycolide, 0.1-10 parts of auxiliary agent and 0.01-3 parts of initiator;
the auxiliary agent is cardanol glycidyl Ether (ECA);
The structural formula of the cardanol glycidyl ether is Wherein n=0, 2, 4 or 6;
when n=0, -C 15H31-n has the formula
When n=2, -C 15H31-n has the formula
When n=4, -C 15H31-n has the formula
When n=6, -C 15H31-n has the formula
The cardanol glycidyl ether comprises the following components in percentage by weight:
n=0 0-10%, And is not 0;
n=2 0-54%, And is not 0;
n=4 0-43%, And is not 0;
n=6 0 To 61%, and not 0.
As a preferred embodiment of the invention, the melt index of the polyglycolide is 5-25 g/10min, and the number average molecular weight is 116239-152380g/mol.
As a preferred embodiment of the present invention, the peroxide initiator is bis-t-butylperoxycumene, dicumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, dibenzoyl peroxide or 1, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane.
The invention also provides a preparation method of the high-melt-strength polyglycolide material, which comprises the following steps:
And uniformly mixing the polyglycolide, the auxiliary agent and the initiator to obtain a mixed material, and carrying out melt extrusion on the mixed material to obtain the high-melt-strength polyglycolide material.
The reaction equation in the reaction system is as follows:
when n=0, the reaction equation is:
when n=2, the reaction equation is:
when n=4, the reaction equation is:
when n=6, the reaction equation is:
Wherein the structural formula of O-R-O is as follows:
(when the peroxide initiator is di-t-butylperoxyisopropyl benzene);
(when the peroxide initiator is dicumyl peroxide);
(when the peroxide initiator is 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane);
(when the peroxide initiator is 1, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane);
Or (b) (When the peroxide initiator is dibenzoyl peroxide).
In a preferred embodiment of the invention, the mixing is performed in a high-speed mixer, wherein the rotation speed of the mixing is 500-2000 rpm, and the time is 5-15 min.
As a preferable embodiment of the invention, the melt extrusion is performed in an internal mixer or a twin-screw extruder, wherein the temperature of the melt extrusion is 230-260 ℃, the rotating speed is 90-200 rpm, and the time is 1-5 min.
The invention also provides application of the high melt strength polyglycolide material in the fields of agricultural production, food packaging or biomedicine.
The technical scheme of the invention is further described by the following specific examples.
Each of the raw materials used in the examples of the present invention was commercially available, wherein the PGA raw material had a melt index (MFR) of 15.8g/10min, which was purchased from Shanghai Pu Jing chemical technology Co.
N=0 in cardanol glycidyl etherThe content of (2) is 0-10wt%, n=2The content of (2) is 0-54 wt%, n=4The content of (2) is 0-43 wt%, n=6The content of the cardanol glycidyl ether is 0-61 wt%, and the cardanol glycidyl ether is purchased from Caridex chemical bead sea Co.
Example 1
100G of polyglycolide, 0.1g of auxiliary agent cardanol glycidyl ether (wherein the content of n=0 component is 3wt%, the content of n=2 component is 40wt%, the content of n=4 component is 37wt%, the content of n=6 component is 20 wt%) and 0.05g of initiator bis-tert-butyl peroxyisopropyl benzene are added into a high-speed mixer, the rotation speed of the mixer is 500rpm, the mixing time is 15min, a mixed material is obtained, the mixed material is put into a double screw extruder for melt extrusion, the melt extrusion temperature is 240 ℃, the rotation speed of a host machine is 100rpm, and the extrusion time is 3min, so that the cardanol glycidyl ether grafted high melt strength polyglycolide material can be obtained.
Example 2
100G of polyglycolide, 3.5g of auxiliary agent cardanol glycidyl ether (wherein the content of n=0 component is 1wt%, the content of n=2 component is 37wt%, the content of n=4 component is 23wt%, the content of n=6 component is 39 wt%) and 1.2g of initiator dicumyl peroxide are added into a high-speed mixer, the rotating speed of the mixer is 800rpm, the mixing time is 12min, a mixed material is obtained, the mixed material is put into a double-screw extruder for melt extrusion, the melt extrusion temperature is 250 ℃, the rotating speed of a host machine is 100rpm, and the extrusion time is 3min, so that the cardanol glycidyl ether grafted high-melt-strength polyglycolide material can be obtained.
Example 3
100G of polyglycolide, 6.0g of auxiliary agent cardanol glycidyl ether (wherein the content of n=0 component is 2wt%, the content of n=2 component is 30wt%, the content of n=4 component is 21wt%, the content of n=6 component is 47 wt%) and 2.0g of initiator 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane are added into a high-speed mixer, the rotating speed of the mixer is 1500rpm, the mixing time is 10min, mixed materials are obtained, the mixed materials are put into a double-screw extruder for melt extrusion, the melt blending temperature is 260 ℃, the host rotating speed is 90rpm, and the extrusion time is 2min, so that the cardanol glycidyl ether grafted high-melt strength polyglycolide material can be obtained.
Example 4
100G of polyglycolide, 8.5g of auxiliary agent cardanol glycidyl ether (wherein the content of n=0 component is 3wt%, the content of n=2 component is 22wt%, the content of n=4 component is 33wt%, the content of n=6 component is 42 wt%) and 3.0g of initiator dibenzoyl peroxide are added into a high-speed mixer, the rotation speed of the mixer is 2000rpm, the mixing time is 8min, a mixed material is obtained, the mixed material is put into a double-screw extruder for melt extrusion, the melt blending temperature is 220 ℃, the rotation speed of a host machine is 150rpm, and the extrusion time is 4min, so that the cardanol glycidyl ether grafted high-melt-strength polyglycolide material can be obtained.
Example 5
100G of polyglycolide, 10.0g of auxiliary agent cardanol glycidyl ether (wherein the content of n=0 component is 3wt%, the content of n=2 component is 40wt%, the content of n=4 component is 27wt%, the content of n=6 component is 30 wt%) and 2.5g of initiator 1, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane are added into a high-speed mixer, the rotating speed of the mixer is 1000rpm, the mixing time is 8min, mixed materials are obtained, the mixed materials are put into a double-screw extruder for melt extrusion, the melt blending temperature is 240 ℃, the rotating speed of a host is 130rpm, and the extrusion time is 5min, so that the cardanol glycidyl ether grafted high-melt strength polyglycolide material can be obtained.
Example 6
The only difference from example 1 is that the melt extrusion temperature was 250℃and the host rotation speed was 200rpm.
Example 7
The only difference from example 2 is that the mixing speed is 2000rpm and the mixing time is 5min.
Comparative example 1
The same as in example 1, except that cardanol glycidyl ether was replaced with cardanol in equal amount(R 1 is-C 15H31-n in which the content of the component of n=0 is 3wt%, the content of the component of n=2 is 40wt%, the content of the component of n=4 is 37wt%, and the content of the component of n=6 is 20 wt%).
Comparative example 2
The only difference from example 1 is that the cardanol glycidyl ether was replaced by pentaerythritol triacrylate (PETA) in equal amounts.
Test case
The grafted polyglycolide materials prepared in examples 1 to 7 and comparative examples 1 to 2 and the raw material PGA were prepared into mechanical bars by a micro injection molding machine, specifically, the samples were pulverized and then melted at 265 ℃ for 4min and then injection molded, in the injection molding process, the mold temperature was 90 ℃, the injection molding pressure was 650bar, the dwell pressure was 600bar, the injection molding time was 25s, and the dwell time was 20s. The impact spline is obtained by milling an A-shaped notch with the depth of 2mm by adopting a V-shaped notch machine after the injection molding of the curved spline. All bars were subjected to mechanical properties testing after 48h storage at 23 ℃ using ISO 527, the specific results are shown in table 1 and figures 1-3. Wherein the melt strength in Table 1 is calculated from the melt flow index MFR value (when the polymer is extruded from the melt flow tester, the melt viscosity at an extremely low shear rate can be calculated by measuring the change in diameter of the extruded portion, and the melt viscosity calculated in this way is referred to as the melt strength).
TABLE 1 Performance data of PGA's of examples and comparative examples
FIG. 1 is a graph showing the complex viscosity as a function of frequency (which characterizes the melt strength of the polymer) of the grafted PGA of examples 1-2 and comparative examples 1-2, as well as pure PGA (raw PGA) in dynamic rheology tests.
As can be seen from the data in Table 1 and FIG. 1, the polyglycolide material prepared by the invention has the characteristic of high melt strength, the melt strength of the PGA after grafting modification is obviously improved, the maximum can be improved to more than 2 times of that of ungrafted PGA, and the impact strength is also greatly improved, thus showing that the effect of grafting modification is obvious. Although the comparative example showed some improvement in the melt strength of PGA, the effect was far inferior to that of the example.
FIG. 2 is a Cole-Cole plot of the grafted PGA of examples 1-2 and comparative examples 1-2, together with pure PGA, the Cole-Cole plot generally being used to distinguish between linear and nonlinear structures of a polymer, the Cole-Cole plot of a linear polymer being nearly semicircular, whereas for a nonlinear structure, a larger radius of the plot indicates more branching of the polymer. As can be seen from fig. 2, the radius of the curve of the example is significantly larger than that of the comparative example.
FIG. 3 is a graph showing relaxation time spectra of the grafted PGA of examples 1-2 and comparative examples 1-2 and pure PGA. As can be seen from fig. 3, the relaxation time of the example grafted PGA was longer than that of the comparative example grafted PGA under the same τ condition.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
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