CN100535050C - Unsaturated monopol polyester foaming plastic and preparation method thereof - Google Patents
Unsaturated monopol polyester foaming plastic and preparation method thereof Download PDFInfo
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- CN100535050C CN100535050C CNB2007100283157A CN200710028315A CN100535050C CN 100535050 C CN100535050 C CN 100535050C CN B2007100283157 A CNB2007100283157 A CN B2007100283157A CN 200710028315 A CN200710028315 A CN 200710028315A CN 100535050 C CN100535050 C CN 100535050C
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- viscotrol
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- 229920003023 plastic Polymers 0.000 title claims abstract description 61
- 239000004033 plastic Substances 0.000 title claims abstract description 61
- 238000005187 foaming Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 13
- 230000005404 monopole Effects 0.000 title claims description 12
- 229920000728 polyester Polymers 0.000 title claims description 12
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003381 stabilizer Substances 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- 239000004359 castor oil Substances 0.000 claims description 27
- 235000019438 castor oil Nutrition 0.000 claims description 27
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 27
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical class CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 24
- -1 maleic anhydride modified Viscotrol C Chemical class 0.000 claims description 24
- 150000002148 esters Chemical class 0.000 claims description 20
- 239000006260 foam Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 238000009775 high-speed stirring Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- 238000010907 mechanical stirring Methods 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 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 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003377 acid catalyst Substances 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 5
- 229920000053 polysorbate 80 Polymers 0.000 claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 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 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 2
- MEJAPGGFIJZHEJ-UHFFFAOYSA-N 5-acetamido-1,3,4-thiadiazole-2-sulfonyl chloride Chemical compound CC(=O)NC1=NN=C(S(Cl)(=O)=O)S1 MEJAPGGFIJZHEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000005147 toluenesulfonyl group Chemical group C=1(C(=CC=CC1)S(=O)(=O)*)C 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 125000005587 carbonate group Chemical group 0.000 claims 1
- 150000003997 cyclic ketones Chemical class 0.000 claims 1
- 238000005502 peroxidation Methods 0.000 claims 1
- 229920006305 unsaturated polyester Polymers 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 8
- 230000006835 compression Effects 0.000 abstract description 4
- 238000007906 compression Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000012856 packing Methods 0.000 abstract description 2
- 235000004443 Ricinus communis Nutrition 0.000 abstract 3
- 239000004088 foaming agent Substances 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 description 9
- 239000003643 water by type Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000002689 soil Substances 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical class OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 235000021281 monounsaturated fatty acids Nutrition 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
A castor unsaturated polyester foaming plastic and production are disclosed. The foaming plastic consists of modified castor resin 100 proportion, vinyl monomer 5-60 proportion, foaming agent 1-15 proportion, foaming stabilizer 0.5-5 proportion, evocating agent 0.5-10 proportion, improver 0-10 proportion, water 0-15 proportion and cross-linking monomer 0-5 proportion. It introduces activated double bond from castor molecular chain. The density of foaming plastic is between 0.1g/cm 3-0.4g/ cm 3, compression strength at 25% strain is between 10-900kPa. It's soft and has semi-hard foaming plastic performance and can be used for packing material, furniture materials or shock-reducing foaming material.
Description
Technical field
The present invention relates to a kind of porous plastics, specifically, relate to a kind of unsaturated monopol polyester foaming plastic and preparation method thereof.
Technical background
Porous plastics has been widely used in each field such as packing, electrical equipment, furniture, automobile as a kind of important macromolecular material.The conventional foam plastics are many to be that main raw material prepares with the petroleum-based products, and it is difficult degradation under field conditions (factors), is the one of the main reasons that causes white pollution.For this reason, substituting the petroleum base porous plastics with Biodegradable foam plastic is development in future trend.It is a lot of to utilize vegetables oil instead of part petroleum to prepare the research of macromolecular material in recent years, is that main raw material prepares the method for degradable sponge plastics for addressing the above problem the approach that provides feasible with vegetables oil (as Viscotrol C and soybean wet goods) wherein.
Viscotrol C has typical unsaturated fatty acids triglyceride structure as a kind of natural polyol.Research in the past is verified, and the urethane foam prepared by Viscotrol C has biological degradability.Yet this method mainly is the hydroxyl that utilizes in the Viscotrol C molecule, with the synthetic compound isocyanate reaction, and preparation polyurethane semi-rigid foam plastics.Because the reaction in 1: 1 in molar ratio of hydroxyl and isocyanic ester, so the large usage quantity of isocyanic ester, the ratio of crude vegetal is not high in the porous plastics, is unfavorable for reducing product cost, is unfavorable for the biological degradability of porous plastics yet.In view of this, be necessary development of new Viscotrol C porous plastics and technology of preparing thereof.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of unsaturated monopol polyester foaming plastic of fully biodegradable is provided.
Another object of the present invention provides the preparation method of above-mentioned unsaturated monopol polyester foaming plastic.
To achieve these goals, unsaturated monopol polyester foaming plastic of the present invention is that component reaction by following parts by weight obtains:
Modified castor oil resin 100
Vinyl monomer 5~60
Whipping agent 1~15
Suds-stabilizing agent 0.5~5
Initiator 0.5~10
Promotor 0~10
Water 0~15
Cross-linking monomer 0~5
In above-mentioned porous plastics, described modified castor oil resin is meant the carboxyl acid modified Viscotrol C that utilizes acid anhydrides or contain unsaturated double-bond, thereby introduces activity double key in Viscotrol C, prepares modified castor oil resin (similar unsaturated polyester).The preferred maleic anhydride modified Viscotrol C resin of modified castor oil resin of the present invention, acrylic acid modified Viscotrol C resin or toxilic acid half ester modified castor oil resin.The preparation method of described maleic anhydride modified Viscotrol C resin is: maleic anhydride and Viscotrol C adding in 2.5: 1 in molar ratio are equipped with in the four-hole bottle of thermometer, mechanical stirring and reflux condensing tube, the adding mass percent is 0~1% catalyst n, the N dimethyl benzylamine, be heated to 80 ℃~120 ℃ reactions 5~9 hours, can obtain maleic anhydride modified Viscotrol C resin;
The preparation method of described acrylic acid modified Viscotrol C resin is: vinylformic acid and Viscotrol C 2~3: 1 adding in molar ratio are equipped with in the there-necked flask of thermometer, mechanical stirring and water trap, add mass percent and be 0.5~1% acid catalyst and mass percent and be 0.2% Resorcinol, add the cyclic hydrocarbon solvent again, under reflux temperature, back flow reaction 9~12 hours, product rotary evaporation obtain acrylic acid modified Viscotrol C resin after removing and desolvating; Described cyclic hydrocarbon solvent is toluene, benzene or dimethylbenzene; Described acid catalyst is hydrochloric acid, sulfuric acid or tosic acid;
The preparation method of described toxilic acid half ester modified castor oil resin is: with maleic anhydride with after Hydroxyethyl acrylate or hydroxyethyl methylacrylate mixed in 1: 1 in molar ratio, the adding mass percent is 0.2% Resorcinol, under agitation, obtain the toxilic acid half ester in 80~100 ℃ of reactions 5~6 hours; Toxilic acid half ester and Viscotrol C 2~3: 1 adding in molar ratio are equipped with in the there-necked flask of thermometer, mechanical stirring and water trap, adding mass percent is 0.5~1% acid catalyst, add the cyclic hydrocarbon solvent again, under reflux temperature, back flow reaction 9~12 hours, product rotary evaporation obtain toxilic acid half ester modified castor oil resin after removing and desolvating; Described cyclic hydrocarbon solvent is toluene, benzene or dimethylbenzene; Described acid catalyst is hydrochloric acid, sulfuric acid or tosic acid.
In above-mentioned porous plastics, the mixture of one or more in described vinyl monomer preferable methyl methyl acrylate, vinylbenzene, butyl acrylate, methyl acrylate, vinyl acetate, ethyl propenoate, the Hydroxyethyl acrylate.
In above-mentioned porous plastics, preferred carbonate of described whipping agent or sulfonyl hydrazide or its mixture; Described carbonate is volatile salt, yellow soda ash, sodium bicarbonate, lime carbonate or barium carbonate; Described sulfonyl hydrazide is benzol sulfohydrazide or toluene sulfonyl hydrazide.
In above-mentioned porous plastics, described suds-stabilizing agent preferred alkyl phenol polyethenoxy ether (OP) or Tween 80 (tween 80) or its mixture.
In above-mentioned porous plastics, the mixture of one or more in the preferred isopropyl benzene hydroperoxide of described initiator, dicumyl peroxide, benzoyl peroxide, methylethyl ketone peroxide or the cyclohexanone peroxide.
In above-mentioned porous plastics, the preferred 8% cobalt naphthenate (Co of described promotor
2+Content 8%) or 10%N, accelerine styrene solution or its mixture.
In above-mentioned porous plastics, the mixture of one or more in the preferred pentaerythritol triacrylate of described cross-linking monomer, Vinylstyrene, glycol diacrylate, the tri methylol triacrylate.
The preparation method of above-mentioned porous plastics may further comprise the steps:
Each component joined in the container in proportion stir; When being whipping agent with carbonate, above-mentioned mixed solution is heated to 30~80 ℃, add entry after the stirring, after high-speed stirring to mixed solution turns white subsequently, pour into rapidly in the open mold of preheating and foam, after foam-formed, put into 100 ℃~130 ℃ baking oven slakings 1~4 hour, make unsaturated monopol polyester foaming plastic; When being whipping agent with the sulfonyl hydrazide, above-mentioned mixed solution is heated to 90 ℃~120 ℃ following high-speed stirring after turn white, change over to through in the open mold of preheating and foam, after foam rises end, put into 100~130 ℃ of baking oven slakings 1~4 hour, make unsaturated monopol polyester foaming plastic.
Compared with prior art, the present invention has following beneficial effect:
1. structural pair of key activity of contained monounsaturated fatty acid molecule is low in the Viscotrol C, is difficult to and other monomer polymerization reaction take places.But the hydroxyl on the Viscotrol C molecular chain is easy and esterification takes place acid anhydrides (as maleic anhydride), also can with carboxylic acid (as vinylformic acid, toxilic acid half ester etc.) esterification take place under catalyst action, thereby introduce activity double key on its molecular chain.The modified castor oil that contains activity double key, similar performance with traditional unsaturated polyester resin, can with inexpensive vinyl diluting monomer polymerization reaction take place, generate macromolecular material, and further prepare unsaturated monopol polyester foaming plastic by foaming and curing process.Viscotrol C is a renewable resources, and modified castor oil has the completely biodegradable energy, and Viscotrol C unsaturated polyester type porous plastics prepared therefrom has the completely biodegradable energy equally.
2. the prepared porous plastics of the present invention has high cost performance.When being the feedstock production urethane foam with the Viscotrol C in the past, owing to use relatively large isocyanic ester, and isocyanic ester costs an arm and a leg, production cost is higher.But it is all lower that the present invention prepares the price of porous plastics desired raw material, and the kind of diluting monomer is more, can adjust the soft or hard degree of porous plastics as required flexibly.
3. the prepared porous plastics density of the present invention is at 0.1g/cm
3~0.4g/cm
3Between, compressive strength has the feature of flexibility or semi-rigid foamed plastics during 25% strain between 10kPa~900kPa, can be used for wrapping material, furniture material or as automobile shock porous plastics etc.
4. the prepared foam materials of the present invention belongs to unsaturated polyester type porous plastics category, this porous plastics possesses physics, the mechanical property of similar traditional porous plastics based on oil, has excellent specific properties such as low cost, biodegradable, content of vegetable oil height simultaneously.
Embodiment
Following umber is meant parts by weight.
Embodiment 1:
Get 100 parts of Viscotrol C, 26.5 parts of maleic anhydrides addings are equipped with in the four-hole bottle of thermometer, mechanical stirring and reflux condensing tube, and oil bath is heated to 120 ℃ of reactions 6 hours, and the acid number of measuring reaction system is 118mgKOH/g.Stop heating, allow reaction product naturally cool to room temperature, obtain maleic anhydride modified Viscotrol C resin.Recording its apparent viscosity under 30 ℃ is 6850mPa.s.
Embodiment 2:
Get 100 parts of Viscotrol C, 26.5 part maleic anhydride, 0.2 part N, the N dimethyl benzylamine adds and is equipped with in the four-hole bottle of thermometer, mechanical stirring and reflux condensing tube, and oil bath is heated to 90 ℃ of reactions 9 hours, the acid number of measuring reaction system is 115mgKOH/g, stop heating, allow reaction product naturally cool to room temperature, obtain maleic anhydride modified Viscotrol C resin.Recording its apparent viscosity under 30 ℃ is 4850mPa.s.
Embodiment 3:
Get 100 parts of Hydroxyethyl acrylates, 84.5 parts of maleic anhydrides, 0.369 part of Resorcinol adds and is equipped with in the there-necked flask of thermometer, mechanical stirring and reflux condensing tube, and oil bath is heated to 90 ℃ of reactions 6 hours.Obtain the toxilic acid half ester, the product acid number is 290mgKOH/g.
Embodiment 4:
Get 100 parts of embodiment 3 prepared toxilic acid half esters, 184 parts of Viscotrol C, tosic acid 1.5 minutes, 200 parts of toluene add thermometer are housed, in the there-necked flask of mechanical stirring and water trap, in 112 ℃ of reactions 11 hours.The product rotary evaporation removes and desolvates, and obtains toxilic acid half ester modified castor oil resin, and its acid number is 28.3mgKOH/g.Recording its apparent viscosity under 30 ℃ is 4100mPa.s.
Embodiment 5:
Get 100 parts of Viscotrol C, 20 parts in vinylformic acid, 0.7 part of tosic acid, 0.24 part of Resorcinol, 90 parts of dimethylbenzene add thermometer are housed, in the there-necked flask of mechanical stirring and water trap, in 145 ℃ of reactions 10 hours.The product rotary evaporation removes and desolvates, and obtains acrylic acid modified Viscotrol C resin, and its acid number is 36mgKOH/g.Recording its apparent viscosity under 30 ℃ is 3200mPa.s.
Embodiment 6:
Get 100 parts of embodiment 1 prepared maleic anhydride modified Viscotrol C resins, 10 parts of vinylbenzene, 5 parts in yellow soda ash, 3 parts of benzoyl peroxides, 2 parts of suds-stabilizing agents (OP-10), 3 part 10% N, the accelerine styrene solution places beaker, after stirring, place the waters to be heated to 50 ℃, add 10 parts of water in system, high-speed stirring is poured free foaming in the mould that has been preheated to 50 ℃ rapidly into after turn white.After the foam rising finishes, put into 120 ℃ of baking oven after fixing and promptly got modified castor oil unsaturated polyester type porous plastics in 2 hours, its performance sees Table 1.
Embodiment 7:
Get 100 parts of the prepared maleic anhydride modified Viscotrol C resins of embodiment 1,25 parts of vinylbenzene, 5 parts in yellow soda ash, 3 parts of benzoyl peroxides, 2 parts of suds-stabilizing agents (OP-10), 3 part 10% N, the accelerine styrene solution places beaker, after stirring, place the waters to be heated to 50 ℃, add 10 parts of water in system, high-speed stirring is poured free foaming in the mould that has been preheated to 50 ℃ rapidly into after turn white.After the foam rising finishes, put into 120 ℃ of baking oven after fixing and promptly got modified castor oil unsaturated polyester type porous plastics in 2 hours, its performance sees Table 1.
Embodiment 8:
Get 100 parts of embodiment 1 prepared maleic anhydride modified Viscotrol C resins, 50 parts of vinylbenzene, 7 parts in lime carbonate, 5 parts of benzoyl peroxides, 3 parts of suds-stabilizing agents (OP-10), place beaker, after stirring, place the waters to be heated to 75 ℃, in system, add 10 parts of water, high-speed stirring is poured free foaming in the mould that has been preheated to 75 ℃ rapidly into after turn white.After the foam rising finishes, put into 120 ℃ of baking oven after fixing and promptly got modified castor oil unsaturated polyester type porous plastics in 2 hours, its performance sees Table 1.
Embodiment 9:
Get 100 parts of embodiment 2 prepared maleic anhydride modified Viscotrol C resins, 50 parts of methyl methacrylates, 7 parts of sodium bicarbonates, 5 parts of benzoyl peroxides, 4 parts of suds-stabilizing agents (OP-10), 5 part 10% N, the accelerine styrene solution places beaker, after stirring, place the waters to be heated to 70 ℃, add 10 parts of water in system, high-speed stirring is poured free foaming in the mould that has been preheated to 70 ℃ rapidly into after turn white.After the foam rising finishes, put into 120 ℃ of degree baking oven after fixing and promptly got modified castor oil unsaturated polyester type porous plastics in 2 hours, its performance sees Table 1.
Embodiment 10:
Get 100 parts of embodiment 2 prepared maleic anhydride modified Viscotrol C resins, 50 parts of vinylbenzene, 5 parts of sodium bicarbonates, 6 parts of methylethyl ketone peroxides, 3 parts of suds-stabilizing agents (OP-10), 5 parts of cobalt naphthenates place beaker, after stirring, place the waters to be heated to 40 ℃, in system, add 5 parts of water, high-speed stirring is poured free foaming in the mould that has been preheated to 40 ℃ rapidly into after turn white.After the foam rising finishes, put into 120 ℃ of baking oven after fixing and promptly got modified castor oil unsaturated polyester type porous plastics in 2 hours, its performance sees Table 1.
Embodiment 11:
Get 100 parts of embodiment 4 prepared toxilic acid half ester modified castor oil resins, 25 parts of vinylbenzene, 2 parts of sodium bicarbonates, cyclohexanone peroxide is stuck with paste 6 parts, 3 parts of suds-stabilizing agents (OP-10), 4 parts of cobalt naphthenates, 2 part 10% N, the accelerine styrene solution places beaker, stir, place the waters to be heated to 35 ℃ after, in system, add 5 parts of water, high-speed stirring is poured free foaming in the mould that has been preheated to 40 ℃ rapidly into after turn white.After the foam rising finishes, put into 120 ℃ of baking oven after fixing and promptly got modified castor oil unsaturated polyester type porous plastics in 2 hours, its performance sees Table 1.
Embodiment 12:
Get 100 parts of embodiment 1 prepared maleic anhydride modified Viscotrol C resins, 50 parts of vinylbenzene, 4 parts of pentaerythritol triacrylates, 0.5 part of sodium bicarbonate, 5 parts of benzol sulfohydrazides, 3 parts of isopropyl benzene hydroperoxides, 3 parts of suds-stabilizing agents (tween-80), 1 part 10% N, the accelerine styrene solution places beaker, after stirring, places oily territory to be heated to 105 ℃ in beaker, high-speed stirring is poured free foaming in the mould that has been preheated to 105 ℃ rapidly into after turn white.After the foam rising finishes, put into 120 ℃ of baking oven after fixing and promptly got modified castor oil unsaturated polyester type porous plastics in 2 hours, its performance sees Table 1.
Embodiment 13:
Get 100 parts of embodiment 4 prepared toxilic acid half ester modified castor oil resins, 20 parts of vinylbenzene, 4 parts in yellow soda ash, 4 parts of benzoyl peroxides, 2 parts of suds-stabilizing agents (OP-10), 3 part 10% N, the accelerine styrene solution places beaker, after stirring, after placing the waters to be heated to 66 ℃, add 6 parts of water in system, high-speed stirring is poured free foaming in the mould that has been preheated to 70 ℃ rapidly into after turn white.After the foam rising finishes, put into 120 ℃ of baking oven after fixing and promptly got modified castor oil unsaturated polyester type porous plastics in 2 hours, its performance sees Table 1.
Embodiment 14:
Get 100 parts of embodiment 5 prepared acrylic acid modified Viscotrol C resins, 20 parts of vinylbenzene, 5 parts in yellow soda ash, 3 parts of benzoyl peroxides, 2 parts of suds-stabilizing agents (tween-80), 5 part 10% N, the accelerine styrene solution places beaker, after stirring, after placing the waters to be heated to 66 ℃, add 6 parts of water in system, high-speed stirring is poured free foaming in the mould that has been preheated to 70 ℃ rapidly into after turn white.After the foam rising finishes, put into 120 ℃ of baking oven after fixing and promptly got modified castor oil unsaturated polyester type porous plastics in 2 hours, its performance sees Table 1.
Table 1: the mechanical property and the degradation property of modified castor oil unsaturated polyester type porous plastics
Embodiment | Density (g/cm 3) | Modulus of compression (MPa) | 10% strain compression intensity (kPa) | 25% strain compression intensity (kPa) | Soil buries 90 days rate of weight loss (%) |
6 | 0.191 | 0.29 | 13.4 | 26.2 | 31.62 |
7 | 0.2 | 0.43 | 32.1 | 47.5 | 23.81 |
8 | 0.196 | 1.7 | 95 | 121.54 | 13.1 |
9 | 0.121 | 0.18 | 9.2 | 15.3 | 16.2 |
10 | 0.165 | 1.31 | 78.2 | 99.54 | 12.8 |
11 | 0.376 | 8.74 | 634 | 741.2 | 21.85 |
12 | 0.296 | 5.9 | 265.3 | 282 | 13.58 |
13 | 0.213 | 0.85 | 58.72 | 89 | 25.83 |
14 | 0.16 | 0.58 | 41 | 69.65 | 27.12 |
Annotate: rate of weight loss (%)=(weight/soil that 1-soil buries the back porous plastics bury before the weight of porous plastics) * 100
Claims (6)
1. unsaturated monopol polyester foaming plastic is characterized in that being obtained by the component reaction of following parts by weight:
Modified castor oil resin 100
Vinyl monomer 5~60
Whipping agent 1~15
Suds-stabilizing agent 0.5~5
Initiator 0.5~10
Promotor 0~10
Water 0~15
Cross-linking monomer 0~5;
Described modified castor oil resin is maleic anhydride modified Viscotrol C resin, acrylic acid modified Viscotrol C resin or toxilic acid half ester modified castor oil resin;
The preparation method of described maleic anhydride modified Viscotrol C resin is: maleic anhydride and Viscotrol C adding in 2.5: 1 in molar ratio are equipped with in the four-hole bottle of thermometer, mechanical stirring and reflux condensing tube, the adding mass percent is 0~1% catalyst n, the N dimethyl benzylamine, be heated to 80 ℃~120 ℃ reactions 5~9 hours, can obtain maleic anhydride modified Viscotrol C resin;
The preparation method of described acrylic acid modified Viscotrol C resin is: vinylformic acid and Viscotrol C 2~3: 1 adding in molar ratio are equipped with in the there-necked flask of thermometer, mechanical stirring and water trap, add mass percent and be 0.5~1% acid catalyst and mass percent and be 0.2% Resorcinol, add the cyclic hydrocarbon solvent again, reacted 9~12 hours down in reflux temperature, the product rotary evaporation obtains acrylic acid modified Viscotrol C resin after removing and desolvating; Described cyclic hydrocarbon solvent is toluene, benzene or dimethylbenzene; Described acid catalyst is hydrochloric acid, sulfuric acid or tosic acid;
The preparation method of described toxilic acid half ester modified castor oil resin is: with maleic anhydride with after Hydroxyethyl acrylate or hydroxyethyl methylacrylate mixed in 1: 1 in molar ratio, the adding mass percent is 0.2% Resorcinol, under agitation, obtain the toxilic acid half ester in 80~100 ℃ of reactions 5~6 hours; Toxilic acid half ester and Viscotrol C 2~3: 1 adding in molar ratio are equipped with in the there-necked flask of thermometer, mechanical stirring and water trap, adding mass percent is 0.5~1% acid catalyst, add the cyclic hydrocarbon solvent again, reacted 9~12 hours down in reflux temperature, the product rotary evaporation obtains toxilic acid half ester modified castor oil resin after removing and desolvating, and described cyclic hydrocarbon solvent is toluene, benzene or dimethylbenzene; Described acid catalyst is hydrochloric acid, sulfuric acid or tosic acid;
Described vinyl monomer is one or more the mixture in methyl methacrylate, vinylbenzene, butyl acrylate, methyl acrylate, vinyl acetate, ethyl propenoate, the Hydroxyethyl acrylate;
Described cross-linking monomer is one or more the mixture in pentaerythritol triacrylate, Vinylstyrene, glycol diacrylate, the tri methylol triacrylate.
2. porous plastics as claimed in claim 1 is characterized in that, described whipping agent is carbonate or sulfonyl hydrazide or its mixture; Described carbonate is volatile salt, yellow soda ash, sodium bicarbonate, lime carbonate or barium carbonate; Described sulfonyl hydrazide is benzol sulfohydrazide or toluene sulfonyl hydrazide.
3. porous plastics as claimed in claim 1 is characterized in that, described suds-stabilizing agent is alkylphenol polyoxyethylene or Tween 80 or its mixture.
4. porous plastics as claimed in claim 1 is characterized in that, described initiator is one or more the mixture in isopropyl benzene hydroperoxide, dicumyl peroxide, benzoyl peroxide, methylethyl ketone peroxide or the peroxidation cyclic ketones.
5. porous plastics as claimed in claim 1 is characterized in that, described promotor is 8% cobalt naphthenate or 10%N, accelerine styrene solution or its mixture.
6. the preparation method of the described porous plastics of claim 1 is characterized in that may further comprise the steps:
Each component joined in the container in proportion stir; When being whipping agent with carbonate, above-mentioned mixed solution is heated to 30~80 ℃, add entry after the stirring, after high-speed stirring to mixed solution turns white subsequently, pour into rapidly in the open mold of preheating and foam, after foam-formed, put into 100 ℃~130 ℃ baking oven slakings 1~4 hour, make unsaturated monopol polyester foaming plastic; When being whipping agent with the sulfonyl hydrazide, above-mentioned mixed solution is heated to 90 ℃~120 ℃ following high-speed stirring after turn white, change over to through in the open mold of preheating and foam, after foam rises end, put into 100~130 ℃ of baking oven slakings 1~4 hour, make unsaturated monopol polyester foaming plastic.
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CN106519097A (en) * | 2016-10-28 | 2017-03-22 | 中国科学院新疆理化技术研究所 | Synthesis method for castoryl maleate-styrene copolymer |
CN109401261A (en) * | 2018-11-07 | 2019-03-01 | 南昌航空大学 | One kind having the function of that oxygen unsaturated polyester resin foamed material and preparation method are put in oxygen uptake |
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CN1123805A (en) * | 1994-10-06 | 1996-06-05 | 辽宁国际华侨经贸总公司 | Multifunctional network interpenetrating composition |
US6225485B1 (en) * | 1999-06-29 | 2001-05-01 | Isp Investments Inc. | High purity adduct of castor oil and maleic anhydride |
US6235916B1 (en) * | 1996-12-24 | 2001-05-22 | University Of Southern Mississippi | Internally plasticizing and crosslinkable monomers and applications thereof |
CN1362452A (en) * | 2002-01-17 | 2002-08-07 | 雷传金 | Caster oil type polyurethane material and its prepn |
US6727314B2 (en) * | 2001-12-13 | 2004-04-27 | Basf Ag | Crosslinking systems for acrylic latex films |
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CN1123805A (en) * | 1994-10-06 | 1996-06-05 | 辽宁国际华侨经贸总公司 | Multifunctional network interpenetrating composition |
US6235916B1 (en) * | 1996-12-24 | 2001-05-22 | University Of Southern Mississippi | Internally plasticizing and crosslinkable monomers and applications thereof |
US6225485B1 (en) * | 1999-06-29 | 2001-05-01 | Isp Investments Inc. | High purity adduct of castor oil and maleic anhydride |
US6727314B2 (en) * | 2001-12-13 | 2004-04-27 | Basf Ag | Crosslinking systems for acrylic latex films |
CN1362452A (en) * | 2002-01-17 | 2002-08-07 | 雷传金 | Caster oil type polyurethane material and its prepn |
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