CN114292366B - Preparation method of degradable bio-based unsaturated polyester/whisker composite material - Google Patents
Preparation method of degradable bio-based unsaturated polyester/whisker composite material Download PDFInfo
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- CN114292366B CN114292366B CN202210084091.6A CN202210084091A CN114292366B CN 114292366 B CN114292366 B CN 114292366B CN 202210084091 A CN202210084091 A CN 202210084091A CN 114292366 B CN114292366 B CN 114292366B
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- 229920006305 unsaturated polyester Polymers 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 14
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003085 diluting agent Substances 0.000 claims abstract description 11
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 10
- 150000002009 diols Chemical class 0.000 claims abstract description 7
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005886 esterification reaction Methods 0.000 claims description 10
- 238000006068 polycondensation reaction Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 7
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical group [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 4
- 239000012773 agricultural material Substances 0.000 claims description 3
- 239000012567 medical material Substances 0.000 claims description 3
- 239000005022 packaging material Substances 0.000 claims description 3
- LAKVEQZDAPXLDL-UHFFFAOYSA-M sodium;ethanol;octadecanoate Chemical compound [Na+].CCO.CCCCCCCCCCCCCCCCCC([O-])=O LAKVEQZDAPXLDL-UHFFFAOYSA-M 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 239000008236 heating water Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 11
- 238000004132 cross linking Methods 0.000 abstract description 7
- 230000002829 reductive effect Effects 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 229920006237 degradable polymer Polymers 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000000051 modifying effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 150000005846 sugar alcohols Polymers 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 18
- 230000015556 catabolic process Effects 0.000 description 17
- 238000006731 degradation reaction Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000002689 soil Substances 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 2
- -1 polybutylene adipate-terephthalate Polymers 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VDHWOHDSOHPGPC-UHFFFAOYSA-N 3,3-dihydroxyoxepan-2-one Chemical compound OC1(O)CCCCOC1=O VDHWOHDSOHPGPC-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a preparation method of a degradable bio-based unsaturated polyester/whisker composite material, and belongs to the technical field of polymer composite materials. The invention synthesizes unsaturated polyester by using bio-based dibasic acid and polycaprolactone diol, and utilizes the long chain structure of polyalcohol to control the crosslinking density and properly increase the flexibility of polymer chains; then preparing the degradable thermosetting polyester with environmental protection, better toughness by using a diluent with low volatility and high activity; and then the aluminum borate whisker is used for modifying unsaturated polyester, so that the mechanical property of the unsaturated polyester is improved, the volume shrinkage rate is reduced, and the degradable polymer composite material with excellent comprehensive properties is prepared. The preparation method provided by the invention has the characteristics of simple synthesis, environment friendliness and easiness in industrialization, and is widely applicable to various parts, disposable products and the like.
Description
Technical Field
The invention relates to a preparation method of a degradable bio-based unsaturated polyester/whisker composite material, belonging to the technical field of polymer composite materials.
Background
In recent years, with the rising of green economy and the rising of environmental awareness, degradable polymer materials have attracted extensive attention in the academic and industrial circles. In particular, thermoplastic polymer materials such as polylactic acid (PLA), polybutylene adipate-terephthalate (PBAT), polybutylene succinate (PBS) and the like have been widely used in the fields of packaging materials, medical materials, agricultural materials and the like. However, the limited biological sources and limited production capacity of the materials can lead to high price and limit the application of the biodegradable thermoplastic polymer materials to a great extent.
In order to meet the increasingly urgent demands of social life on degradable high polymer materials, the preparation and application research of the degradable thermosetting high polymer materials naturally arouses the interests of scientific research institutions and industries. At present, two preparation methods of degradable thermosetting polymer materials are mainly adopted, one is based on a reversible covalent chemical crosslinking polymer, and the material needs to trigger reversible reaction under the action of specific stimulation conditions (such as heat, light, pH) and the like; degradation of the polymer is realized; the method realizes the degradation of the thermosetting material, but has specific requirements on degradation conditions, and the mechanical properties and the like of the material are lost due to the introduction of dynamic bonds. The other is to prepare bio-based thermosetting epoxy, unsaturated polyester, polyurethane and the like, and it is well known that the good mechanical property and heat resistance of the thermosetting material are derived from high crosslinking density; however, for the bio-based thermosetting materials, in order to obtain high degradation rate, the crosslinking degree of the system is often required to be controlled, so that the mechanical properties, heat resistance and other properties of the degradable bio-based thermosetting materials are poorer than those of the traditional thermosetting materials; the degradable bio-based unsaturated polyester is formed by polycondensation of biomass-derived unsaturated dibasic acid and dihydric alcohol or saturated dibasic acid and unsaturated dihydric alcohol, so that partial or full bio-based is realized; however, the mechanical properties and heat resistance are also poor.
Disclosure of Invention
[ technical problem ]
The problems of good degradation performance, mechanical property and heat resistance of the prepared biological-based thermosetting material exist contradiction due to the crosslinking density.
Technical scheme
In order to solve the problems, the invention synthesizes unsaturated polyester by using bio-based dibasic acid and polycaprolactone diol, and uses the long chain structure of polyalcohol to control the crosslinking density and increase the flexibility of polymer chain in proper amount; then preparing the degradable thermosetting polyester with environmental protection, better toughness by using a diluent with low volatility and high activity; and then the aluminum borate whisker is used for modifying unsaturated polyester, so that the mechanical property of the unsaturated polyester is improved, the volume shrinkage rate is reduced, and the degradable polymer composite material with excellent comprehensive properties is prepared. The preparation method provided by the invention has the characteristics of simple synthesis, environment friendliness and easiness in industrialization, and is widely applicable to various parts, disposable products and the like.
A first object of the present invention is to provide a process for preparing a degradable bio-based unsaturated polyester/whisker composite material comprising the steps of:
(1) Preparation of unsaturated polyester by direct esterification polycondensation
Firstly carrying out esterification reaction on bio-based unsaturated dibasic acid and saturated dihydric alcohol, and then carrying out polycondensation reaction to obtain unsaturated polyester;
(2) Preparation of pretreated whiskers
Heating water, adding a pretreatment agent solution, and adjusting the pH to 8-9; adding whisker, reacting, separating solid from liquid, washing and drying to obtain pretreated whisker;
(3) Preparation of bio-based unsaturated polyester/whisker composite material
Adding the pretreated whisker, the diluent, the initiator and the accelerator in the step (2) into the unsaturated polyester in the step (1), uniformly mixing and defoaming; then introducing the mixture into a mould for curing to obtain the bio-based unsaturated polyester/whisker composite material; wherein the addition amount of the pretreatment whisker is 0.5-2wt% of the mass of the unsaturated polyester.
In one embodiment of the present invention, the bio-based unsaturated dibasic acid in the step (1) is one or more of itaconic acid, succinic acid and fumaric acid.
In one embodiment of the present invention, the saturated diol of step (1) is polycaprolactone diol (PCL diol).
In one embodiment of the present invention, the molar ratio of saturated glycol to biobased unsaturated diacid (molar ratio of alkyd) described in step (1) is 1 to 1.3:1, further preferably 1.2:1.
in one embodiment of the present invention, the esterification reaction of step (1) comprises the steps of:
adding catalyst and polymerization inhibitor into bio-based unsaturated dibasic acid and saturated dihydric alcohol, connecting stirrer, water separator, thermometer and condensing unit, and introducing N 2 Reacting for 5-7h at 160-170 ℃, and reacting at constant temperature until no water is produced in the system; wherein the catalyst is tetrabutyl titanate, and the dosage is 0.08-0.12wt% of bio-based unsaturated dibasic acid; the polymerization inhibitor is hydroquinone, and the mass is 0.08-0.12wt% of bio-based unsaturated dibasic acid; further preferred are: reacting for 6 hours at 165 ℃, wherein the catalyst is tetrabutyl titanate, and the dosage is 0.1 weight percent of bio-based unsaturated dibasic acid; the polymerization inhibitor is hydroquinone, and the mass is 0.1wt% of the bio-based unsaturated dibasic acid.
In one embodiment of the present invention, the polycondensation reaction of step (1) comprises the steps of:
reacting the esterification reaction product at 180-190 ℃ under 0.08-0.12MPa for 1.5-2.5h to obtain unsaturated polyester after the reaction is finished; further preferred are: the reaction was carried out at 185℃under 0.1MPa for 2h.
In one embodiment of the invention, the water in step (2) is heated to a temperature of 35-45 ℃, more preferably 40 ℃.
In one embodiment of the present invention, the volume ratio of water to pretreatment solution in step (2) is 18-22:1, further preferably 20:1.
in one embodiment of the present invention, the pretreatment agent in the step (2) is sodium stearate, the pretreatment agent solution is sodium stearate ethanol solution, and the concentration is 0.01-0.1mol/L, and more preferably 0.05mol/L.
In one embodiment of the invention, the pH adjustment in step (2) is carried out by adding sodium hydroxide solution, wherein the concentration of the sodium hydroxide solution is 0.1mol/L.
In one embodiment of the present invention, the whisker in step (2) is an aluminum borate whisker having a length of 20 to 40 μm and a diameter of 1 to 2. Mu.m.
In one embodiment of the invention, the whisker and pretreatment agent solution of step (2) is 1 in g/mL: 1-3, further preferably 1:2.
in one embodiment of the invention, the reaction in step (2) is carried out at 20-30deg.C (ambient temperature) with stirring at 500-600rpm for 35-45min.
In one embodiment of the present invention, the diluent in the step (3) is one or more of dimethyl itaconate, methyl methacrylate and N-vinyl pyrrolidone.
In one embodiment of the present invention, the initiator in step (3) is cyclohexanone peroxide.
In one embodiment of the present invention, the promoter in step (3) is cobalt naphthenate.
In one embodiment of the present invention, the mass ratio of the unsaturated polyester, the pretreated whisker, the diluent, the initiator and the accelerator in the step (3) is 100:0.5-3:20-40:2-3:0.4 to 0.6, more preferably 100:1:30:2.5:0.5.
in one embodiment of the present invention, the defoaming in the step (3) is static defoaming.
In one embodiment of the present invention, the curing in step (3) is performed at 75-85 ℃ for 4-6 hours, followed by 24-30 hours at 20-30 ℃ (normal temperature).
The second object of the invention is a degradable bio-based unsaturated polyester/whisker composite material prepared by the method.
A third object of the present invention is the use of the degradable biobased unsaturated polyester/whisker composite material according to the invention in the field of packaging materials, medical materials and agricultural materials.
In one embodiment of the invention, the packaging field of application includes use for disposable articles.
[ advantageous effects ]
(1) The bio-based degradable unsaturated polyester composite material has the characteristics of good toughness, low volume shrinkage and degradability, and the preparation method has the characteristics of simplicity in operation, environment friendliness and easiness in industrialization.
(2) The invention adopts a direct esterification polycondensation method, uses bio-based itaconic acid and easily depolymerized caprolactone diol to synthesize unsaturated polyester, and has the characteristics of simple synthesis method, easy industrialization and green and environment-friendly product.
(3) According to the invention, the unsaturated polyester is cured and crosslinked by using the diluent N-vinyl pyrrolidone with low volatility and high activity, the cured unsaturated polyester is degraded to about 30% in an aqueous solution with pH value of 12 for 21 days, and the degradation to about 3.5% in soil for 30 days.
(4) The aluminum borate whisker adopted by the invention has the characteristics of relatively low price, excellent mechanical property and low volume shrinkage, when the mass fraction of the aluminum borate whisker is only 1%, the tensile strength of the composite material is 9.7Mpa, the elongation at break is 28.4%, the volume shrinkage is 2.7%, the tensile strength is improved by 16.7% compared with the pure unsaturated polyester, the volume shrinkage is reduced by 55.7%, and the prepared composite material has better mechanical property and low volume shrinkage, thereby widening the application range.
(5) The stress of the bio-based unsaturated polyester/whisker composite material prepared by the invention can reach 9.7MPa; the elongation at break reaches 28.4%; the volume shrinkage can be as low as 2.2%; the thermal decomposition temperature reaches more than 227 ℃ and reaches 237 ℃; about 30% degradation in aqueous solution at ph=12 at 21 d; degradation is about 3.5% in soil for 30 days.
Drawings
FIG. 1 is a Fourier infrared (FT-IR) diagram of an unsaturated polyester of example 1.
Fig. 2 is a graph of the mechanical properties of the composites of examples 1 and 2.
Fig. 3 is a graph of the volumetric shrinkage of the composites of examples 1 and 2.
FIG. 4 is a graph of the gel content of the composites of examples 1 and 2.
Fig. 5 is a thermal decomposition temperature diagram of the composites of examples 1 and 2.
Fig. 6 is a graph of the degradation performance of the composites of examples 1 and 2 at ph=12 buffer solutions.
Fig. 7 is a graph of the degradation performance in soil of the composites of examples 1 and 2.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for better illustration of the invention, and should not be construed as limiting the invention.
The testing method comprises the following steps:
infrared spectrum testing: controlling wave number range of 4000-400cm by using total reflection infrared spectrum diffractometer -1 Infrared spectroscopic analysis was performed.
Testing mechanical properties: the test was performed according to GB/T2567-2008 standard.
Volume shrinkage test: testing was performed according to ANSI/ASTM D6289-1998 standard.
Heat resistance test: the thermogravimetric analyzer TGA/1100SF is used, the heating rate is 10 ℃/min, and the temperature is 50-600 ℃.
Gel content test: the measurement is carried out by Soxhlet extraction, acetone is used as a solvent, extraction is carried out for 24 hours at 80 ℃, and weighing is carried out after full drying.
Degradation performance test:
1. soil degradation experiment: samples of 30mm x 1.5mm are weighed and clamped between copper nets and then buried in flower nursery soil (the depth is about 10-15cm, the ambient temperature is 10-25 ℃ depending on seasons), the samples are taken out at intervals of half a month, washed clean with deionized water, dried in an oven at 40 ℃ for 24 hours, weight loss is tested, and three groups of experiments are performed on each sample, and the results are averaged.
2. Aqueous solution degradation experiments: phosphate buffer solution of ph=12 was prepared first, disc samples (diameter 10mm, thickness about 1 mm) were placed in buffer solution of 20ml ph=12.0 at 37 ℃, samples were taken out every other week, rinsed with deionized water and dried to constant weight. For each sample, three measurements were made and the average value was taken.
Example 1
A method of making a degradable bio-based unsaturated polyester/whisker composite material comprising the steps of:
(1) Preparation of unsaturated polyester by direct esterification polycondensation
According to the molar ratio of 1.2:1, adding PCL glycol and itaconic acid IA into a 250mL four-neck flask, adding tetrabutyl titanate serving as a catalyst with the mass of 0.1wt% of itaconic acid IA and hydroquinone serving as a polymerization inhibitor with the mass of 0.1wt% of itaconic acid IA, connecting a stirrer, a thermometer and a condensing device, and introducing N 2 Protection, reaction for 6h at 165 ℃, and constant temperature reaction until the system does not produceRaw water; then connecting a water ring type vacuum pump, reacting for 2 hours at 185 ℃ under the system pressure of 0.1MPa, reacting at constant temperature, and cooling to room temperature after the reaction is finished to obtain the unsaturated polyester.
(2) Preparation of pretreated whiskers
Heating 80mL of distilled water to 40 ℃, adding 4mL of sodium stearate ethanol solution (0.05 mol/L) and dropwise adding sodium hydroxide solution to control the pH value of the solution to 8-9; adding 2.0g aluminum borate whisker (length 20-40 μm, diameter 1-2 μm) into the solution, stirring at 40 deg.C and 550rpm for 40min, suction filtering, washing and drying to obtain pretreated whisker;
(3) Preparation of bio-based unsaturated polyester/whisker composite material
Adding 1g of pretreatment whisker, 30g N-vinyl pyrrolidone, 2.5g of cyclohexanone peroxide and 0.5g of cobalt naphthenate into 100g of bio-based unsaturated polyester, rapidly and uniformly stirring, standing and defoaming to obtain a mixture; and pouring the mixture into a tetrafluoroethylene mold for curing, taking out the mixture from the mold after curing for 4 hours at 80 ℃, and standing the mixture for 24 hours at normal temperature to obtain the bio-based unsaturated polyester/whisker composite material.
The resulting biobased unsaturated polyester/whisker composite was tested and the test results were shown in fig. 1: as can be seen from fig. 1: the bio-based unsaturated polyester (PIPCL) is compared with itaconic acid IA and PCL glycol, and the infrared spectrum is 3400cm -1 、1626cm -1 、1728cm -1 The variation of the-OH, -c=c-and-c=o peaks indicates successful preparation of unsaturated polyesters.
Example 2
The mass of the pretreated whiskers in example 1 was adjusted to 0, 0.5, 2 and 3g so that the amount of the pretreated whiskers was 0, 0.5%, 2% and 3% of the mass of the bio-based unsaturated polyester, and the other was kept the same as in example 1, to obtain a bio-based unsaturated polyester/whisker composite material.
The biobased unsaturated polyester/whisker composites obtained in examples 1 and 2 were tested as follows:
it can be seen from tables 1 to 3: with the increase of the content of the aluminum borate whisker, the mechanical property of the composite material tends to be increased and then reduced, when the mass fraction of the whisker is 1%, the tensile strength of the composite material is 9.7MPa, the elongation at break is 28.4%, and the volume shrinkage is 2.7%; the gel content of the composite material is higher than 90%, which indicates that the material is basically and completely cured, the thermal decomposition temperature of the material is higher than 220 ℃, and the composite material has good thermal stability; the composite material is degraded by about 30% in an aqueous solution with ph=12 for 21 days; degradation is about 3.5% in soil for 30 days.
TABLE 1 results of tests for mechanical Properties, volume shrinkage and gel content
Table 2 buffer solution degradation mass loss rate (%) at ph=12
| Quality of pretreated whisker (g) | 0d | 7d | 14d | 21d |
| 0 | 0 | 10.46 | 25.9 | 28.38 |
| 0.5 | 0 | 10.47 | 28.0 | 30.3 |
| 1 (example 1) | 0 | 8.7 | 26.15 | 31.45 |
| 2 | 0 | 10.13 | 24.61 | 32.15 |
| 3 | 0 | 8.65 | 26.85 | 29.81 |
TABLE 3 mass loss rate in soil degradation (%)
| Quality of pretreated whisker (g) | 0d | 15d | 30d |
| 0 | 0 | 2.01 | 2.72 |
| 0.5 | 0 | 2.39 | 3.26 |
| 1 (example 1) | 0 | 1.97 | 2.87 |
| 2 | 0 | 2.65 | 3.43 |
| 3 | 0 | 2.7 | 3.56 |
Example 3
The mass of the diluent N-vinylpyrrolidone in example 1 was adjusted to 20 and 40g so that the amount of the diluent was 20% and 40% of the mass of the bio-based unsaturated polyester, and the other was kept the same as in example 1, to obtain a bio-based unsaturated polyester/whisker composite.
The biobased unsaturated polyester/whisker composites obtained in examples 1 and 3 were tested as follows:
TABLE 4 results of tests for mechanical Properties, volume shrinkage, gel content and thermal decomposition temperature
As can be seen from table 4: when the addition amount of the diluent is 30% of the unsaturated polyester, the mechanical property of the composite material is optimal, and the composite material has lower volume shrinkage and good heat resistance.
Comparative example 1
Step (2) of example 1 was omitted, namely: the whiskers were not pretreated and otherwise identical to example 1, resulting in a biobased unsaturated polyester/whisker composite.
Comparative example 2
Step (2) in adjustment example 1 is:
weighing 9g of analytically pure ethanol and 1g of distilled water to prepare a mixed solvent, and dripping glacial acetic acid to adjust the pH value of the solution to 4.0-5.0; 0.5g (5 wt%) of KH-550 (relative to ethanol solution) was dissolved in the mixed solvent under stirring at 500rpm, and then pre-hydrolyzed by stirring with a magnetic stirrer at 500rpm for 1 hour to obtain a pre-hydrolyzed silane coupling agent;
dispersing aluminum borate whisker in distilled water with the mass of 5 times of that of the aluminum borate whisker, rapidly stirring and dispersing, and ultrasonically oscillating for 5min; slowly dripping the silane coupling agent subjected to prehydrolysis under the stirring of 500rpm, stirring for 10min after dripping, and standing for 0.5h to obtain slurry; removing most of water from the slurry by vacuum suction filtration, putting the slurry into a baking oven at 120 ℃ for 24 hours, and scattering the slurry after taking out for standby; obtaining pretreated whiskers; wherein the mass ratio of the aluminum borate whisker to the coupling agent is 2:1;
otherwise, in accordance with example 1, a biobased unsaturated polyester/whisker composite material was obtained.
Comparative example 3
Step (2) in adjustment example 1 is:
firstly, baking the aluminum borate whisker at 80 ℃ for 6 hours; preparing a borate absolute ethanol solution with the concentration of 0.2 mol/L; then pouring the aluminum borate whisker into a borate absolute ethanol solution, stirring for 2 hours at room temperature, standing for 8 hours at room temperature, drying for 2 hours at 80 ℃, drying, sealing and storing to obtain pretreated whisker; wherein the mass ratio of the whisker to the borate is 1:0.5;
otherwise, in accordance with example 1, a biobased unsaturated polyester/whisker composite material was obtained.
The obtained bio-based unsaturated polyester/whisker composite material is tested, and the test result is as follows:
table 5 test results for comparative examples 1, 2 and 3
| Comparative example | Stress (MPa) | Elongation at break (%) | Volume shrinkage (%) | Gel content (%) | Thermal decomposition temperature (. Degree. C.) |
| 1 | 6.2 | 11.9 | 3.9 | 92.7 | 201 |
| 2 | 8.5 | 21.3 | 3.4 | 93.3 | 215 |
| 3 | 7.9 | 19.2 | 3.7 | 92.6 | 202 |
As can be seen from table 5: the whisker in the comparative example 1 has poor modification effect on unsaturated polyester without pretreatment, and the mechanical property and heat resistance of the material are reduced; the pretreatment of aluminum borate whiskers with KH-550 silane coupling agent in comparative example 2 and the borate absolute ethanol solution in comparative example 3 gave better reinforcing effect on unsaturated polyester than whiskers not pretreated, but the use of sodium stearate gave better modifying effect on unsaturated polyester than the pretreatment of whiskers with sodium stearate in example 1.
Comparative example 4
The PCL diol in example 1 was adjusted to butanediol, and the other was the same as in example 1 to obtain a composite material.
And performing performance test on the obtained material, wherein the test result is as follows:
table 6 test results of comparative example 4
As can be seen from table 6: when the dihydric alcohol in the unsaturated polyester is changed from PCL glycol to butanediol, the chemical structure of the dihydric alcohol is changed from long chain to short chain, so that the crosslinking density of the material is improved. Compared with PCL glycol as dihydric alcohol, the tensile strength of the material is 12.3Mpa, the gel content is 96.1%, the thermal decomposition temperature is 239 ℃, but the elongation at break of the material is obviously reduced by 3%, the volume shrinkage is increased by 4.8%, and the degradation performance of the material is inevitably reduced along with the increase of the crosslinking density.
Claims (7)
1. A method of making a degradable bio-based unsaturated polyester/whisker composite material comprising the steps of:
(1) Preparation of unsaturated polyester by direct esterification polycondensation
Firstly carrying out esterification reaction on bio-based unsaturated dibasic acid and saturated dihydric alcohol, and then carrying out polycondensation reaction to obtain unsaturated polyester;
wherein the bio-based unsaturated dibasic acid is itaconic acid; the saturated dihydric alcohol is polycaprolactone diol;
the esterification reaction comprises the following steps:
adding catalyst and polymerization inhibitor into bio-based unsaturated dibasic acid and saturated dihydric alcohol, connecting stirrer, water separator, thermometer and condensing unit, and introducing N 2 Reacting for 5-7h at 160-170 ℃, and reacting at constant temperature until no water is produced in the system;
the polycondensation reaction comprises the following steps:
reacting the esterification reaction product at 180-190 ℃ under 0.08-0.12MPa for 1.5-2.5h to obtain unsaturated polyester after the reaction is finished;
(2) Preparation of pretreated whiskers
Heating water, adding a pretreatment agent solution, and adjusting the pH to 8-9; adding whisker, reacting, separating solid from liquid, washing and drying to obtain pretreated whisker; wherein the pretreatment agent is sodium stearate, the pretreatment agent solution is sodium stearate ethanol solution, and the concentration is 0.01-0.1mol/L; the whisker is aluminum borate whisker with the length of 20-40 mu m and the diameter of 1-2 mu m;
(3) Preparation of bio-based unsaturated polyester/whisker composite material
Adding the pretreated whisker, the diluent, the initiator and the accelerator in the step (2) into the unsaturated polyester in the step (1), uniformly mixing and defoaming; then introducing the mixture into a mould for curing to obtain the bio-based unsaturated polyester/whisker composite material; wherein the addition amount of the pretreatment whisker is 0.5-2wt% of the mass of the unsaturated polyester.
2. The method of claim 1, wherein the molar ratio of saturated glycol to biobased unsaturated diacid of step (1) is 1 to 1.3:1.
3. the method according to claim 1, wherein the mass ratio of the unsaturated polyester, the pretreated whiskers, the diluent, the initiator and the accelerator in the step (3) is 100:0.5-3:20-40:2-3:0.4-0.6.
4. The method of claim 1, wherein the volume ratio of water to pretreatment solution in step (2) is 18-22:1.
5. the method of claim 1, wherein the whisker and pretreatment agent solution of step (2) is 1 in g/mL: 1-3.
6. A degradable biobased unsaturated polyester/whisker composite material prepared by the method of any one of claims 1-5.
7. Use of the degradable biobased unsaturated polyester/whisker composite material according to claim 6 in the fields of packaging materials, medical materials and agricultural materials.
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| CN1693421A (en) * | 2005-06-17 | 2005-11-09 | 浙江大学 | Organic-inorganic fire-retarded high molecular material of few additive high performance |
| CN101165105A (en) * | 2007-10-09 | 2008-04-23 | 沈阳理工大学 | Chemical coating method for modifying surface of magnesium hydroxide whisker material |
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| WO2006053031A2 (en) * | 2004-11-12 | 2006-05-18 | Mayo Foundation For Medical Education And Research | Photocrosslinkable poly(caprolactone fumarate) |
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| CN1693421A (en) * | 2005-06-17 | 2005-11-09 | 浙江大学 | Organic-inorganic fire-retarded high molecular material of few additive high performance |
| CN101165105A (en) * | 2007-10-09 | 2008-04-23 | 沈阳理工大学 | Chemical coating method for modifying surface of magnesium hydroxide whisker material |
| CN104987684A (en) * | 2015-06-05 | 2015-10-21 | 苏州珍展科技材料有限公司 | Unsaturated polyester composite material for bathtub and preparing method thereof |
| CN109354851A (en) * | 2018-09-30 | 2019-02-19 | 濮阳市盛源能源科技股份有限公司 | A kind of preparation method of biology base unsaturated polyester resin flame-retardant composite material |
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