CN105418902A - Tung oil base unsaturated co-ester resin for moulding compound, synthesis method and applications thereof - Google Patents
Tung oil base unsaturated co-ester resin for moulding compound, synthesis method and applications thereof Download PDFInfo
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- CN105418902A CN105418902A CN201511017957.8A CN201511017957A CN105418902A CN 105418902 A CN105418902 A CN 105418902A CN 201511017957 A CN201511017957 A CN 201511017957A CN 105418902 A CN105418902 A CN 105418902A
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- Prior art keywords
- tung oil
- oil base
- reaction
- vinylbenzene
- weight
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- 239000002383 tung oil Substances 0.000 title claims abstract description 91
- 229920005989 resin Polymers 0.000 title claims abstract description 66
- 239000011347 resin Substances 0.000 title claims abstract description 66
- 239000000206 moulding compound Substances 0.000 title claims abstract description 10
- 238000001308 synthesis method Methods 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000047 product Substances 0.000 claims abstract description 32
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 229920005862 polyol Polymers 0.000 claims abstract description 3
- 150000003077 polyols Chemical class 0.000 claims abstract description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 44
- 239000002253 acid Substances 0.000 claims description 42
- 150000002148 esters Chemical class 0.000 claims description 42
- 229940059574 pentaerithrityl Drugs 0.000 claims description 22
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- -1 dihydroxyphenyl propane alcohols Chemical class 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000010189 synthetic method Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 3
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004412 Bulk moulding compound Substances 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 239000003677 Sheet moulding compound 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
- 230000000694 effects Effects 0.000 claims description 3
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 239000003112 inhibitor Substances 0.000 abstract 2
- 238000006116 polymerization reaction Methods 0.000 abstract 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 abstract 1
- 238000007865 diluting Methods 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- 239000007788 liquid Substances 0.000 description 19
- 239000012263 liquid product Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010773 plant oil Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical group OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/47—Polyesters chemically modified by esterification by unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
-
- 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
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a tung oil base unsaturated co-ester resin for moulding compound, a synthesis method and applications thereof. The synthesis method comprises the following steps: making tung oil and polyol carry out alcoholysis reactions in the presence of a catalyst to generate an alcoholysis product namely tung oil base monoglyceride; then adding maleic anhydride, carrying out reactions in the presence of a catalyst and a polymerization inhibitor to generate tung oil base semi-maleate; adding propylene compounds to generate propenyl-maleinized tung oil base unsaturated co-ester; diluting the co-ester by styrene containing a polymerization inhibitor, and evenly dispersing the mixture to obtain the final product. The synthesized tung oil base unsaturated co-ester resin is similar to universal UPR, has excellent mechanical and thermal properties after solidification, can be easily thickened, and can be used as moulding compound.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to the unsaturated altogether ester resin of a kind of tung oil base and synthetic method thereof and application.Resin prepared by the method can be used for preparing sheet/Bulk Molding Compound, and then for industrial circles such as automobile, yacht, electrical equipment, facilities for building.
Background technology
Unsaturated polyester (UnsaturatedPolyester is called for short UPE) refers to by unsaturated dibasic acid (as maleic anhydride), monounsaturated dicarboxylic acid and the dibasic alcohol linear polyester through polycondensation.UPE can obtain unsaturated polyester resin (UnsaturatedPolyesterResin is called for short UPR) after monomer (as the vinylbenzene) dilution containing double bond.Under the effect of initiator and promotor, copolyreaction can be there is and generate 3-D solid structure in this resin, form insoluble not molten thermosetting resin, and there is good mechanical property, thermal characteristics and chemical resistance, be a kind of resin that in composite reinforcing material, usage quantity is maximum, be mainly used in the fields such as building, automobile, boats and ships, daily necessities and common equipment.
Since entering 21st century, due to problems such as the day by day exhausted of fossil resources and environmental pollutions, seeking efficient, cheapness, reproducible alternative materials becomes the task of top priority.As the renewable resources that the world abounds with, crude vegetal due to structure special, itself have certain degradation property, thus by the polymkeric substance of its modification, not only cost is lower, and its waste more can reduce the harm to environment.Therefore, utilize vegetables oil synthesizing new UPR resin, meet the development trend of UPR industry.
Summary of the invention
The technical problem solved: the present invention is intended to overcome that existing plant oil based UPR kind lacks, unsaturated ester resin variety is altogether rare especially and synthetic method is single and increase the molecular functionality of existing tung oil base acid half ester monomer and improve the cross-linking density, performance etc. of corresponding resin.By polystep reaction, improve synthetic method and process, thus a kind of processing ease, constant product quality, the unsaturated ester resin (UPR) altogether of lower-cost a kind of moulding compound tung oil base and synthetic method thereof and application are provided.The synthetic method of this UPR, without the need to using solvent, without waste, meets the Green Development requirement of modern chemical industry.
Technical scheme: the synthetic method of the unsaturated ester resin altogether of a kind of moulding compound tung oil base, preparation process is: (1) is under the effect of acid or basic catalyst, be heated to 150 ~ 250 DEG C of reaction 1 ~ 10h, make tung oil and polyvalent alcohol generation alcoholysis reaction, generate tung oil base mono-glycerides alcoholysis product, catalyst levels is 0.2 ~ 4% of tung oil and total polyol weight; Described polyvalent alcohol is at least one in dihydroxyphenyl propane alcohols, glycerol, tetramethylolmethane; The material molar ratio of described polyvalent alcohol and tung oil is 1:1 ~ 4:1; (2) then add maleic anhydride, the material molar ratio of maleic anhydride and tung oil is 2:1 ~ 10:1, under the existence of catalyzer and stopper, continues heating 50 ~ 200 DEG C, and reaction 1 ~ 10h generates tung oil base acid half ester; Stopper is at least one in Resorcinol, para benzoquinone, BHT, and consumption is 0.1 ~ 1% of raw material gross weight; (3) propene compound is added again, described propene compound is at least one in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, hy-droxybutyl, methacrylate, vinylcarbinol or methacrylic alcohols, the material molar ratio of propene compound and tung oil is 0.5:1 ~ 5:1, continue heating 50 ~ 200 DEG C, reaction 1 ~ 10h, generates the unsaturated ester altogether of propenyl-maleinization tung oil base; Be cooled to 80 ~ 100 DEG C after reaction terminates, add the vinylbenzene being dissolved with stopper and dilute, described vinylbenzene add-on is 30 ~ 60% of the unsaturated ester weight altogether of tung oil base, and stopper is 0.1 ~ 1% of vinylbenzene weight, is uniformly dispersed and obtains end product.
Described basic catalyst is sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium ethylate, potassium ethylate, sodium methylate, potassium methylate or caoxalate; An acidic catalyst is sulfuric acid, hydrochloric acid, nitric acid or sulfonic acid.
Heating temperature described in step (1) is 200 DEG C, and the reaction times is 2h; Described polyvalent alcohol and the material molar ratio of tung oil are 2:1 or 3:1.
The material molar ratio of the maleic anhydride described in step (2) and tung oil is 8:1; Described Heating temperature 100 DEG C, the reaction times is 5h.
Catalyzer described in step (2) is sulfuric acid, tosic acid, sodium hydroxide, N, N-dimethyl benzylamine, triphenylphosphine or Methylimidazole, and consumption is 0.2 ~ 4% of tung oil alcoholysis product and maleic anhydride gross weight.
The material molar ratio of the propene compound described in step (3) and tung oil is 1.5:1.
Heating temperature described in step (3) is 100 DEG C, and the reaction times is 5h.
Vinylbenzene add-on described in step (3) is 40% of the unsaturated ester weight altogether of tung oil base, and stopper is 0.1% of vinylbenzene weight.
The unsaturated ester resin altogether of the tung oil base that described method prepares.
The application of the unsaturated ester resin altogether of described tung oil base in preparation sheet/Bulk Molding Compound.
Beneficial effect:
(1) the unsaturated ester monomer altogether of the tung oil base synthesized by the present invention not only belongs to UPR new variety, in plant oil based UPR, also belong to brand-new kind.
(2) synthetic method used introduces propenyl structure again for first introducing toxilic acid structure, belongs to and adopts first, can offer reference for the synthesis of this type of unsaturated ester altogether; In addition, adopt three-step approach synthetic technology, three steps synthesis can concentrate in one pot to be carried out, processing ease, and the comparatively simple and constant product quality of technique, is easy to industrial expanding production.
(3) the unsaturated altogether ester resin of the tung oil base synthesized by is similar with general UPR, possesses excellent mechanics and thermal property, and be easy to thickening after solidification, can be used as moulding compound use.
Accompanying drawing explanation
Fig. 1 is that (a) TOPERMA composes with the FT-IR of (b) TOPERMA-HEA;
Fig. 2 is TOPERMA's (a) and TOPERMA-HEA (b)
1h-NMR composes;
Fig. 3 is the gel chromatography of TOPERMA and TOPERMA-HEA;
Fig. 4 is the synthetic route of the unsaturated ester monomer altogether of tung oil base toxilic acid-propenyl.
Embodiment
The following examples of the present invention further illustrating only as content of the present invention, can not as perhaps scope in restriction of the present invention.Below in conjunction with embodiment, the invention will be further described.
Embodiment 1 ~ 25
Polyvalent alcohol and the catalyzer of 87.2g tung oil (0.1mol) and calculated amount is added in 250mL tetra-neck round-bottomed flask, as shown in table 1, and load onto airway, thermometer, reflux condensing tube and drying tube.Flask is placed in electric heating cooker, stirs and lead to nitrogen, start reaction.Be cooled to room temperature rapidly at the end of reaction, obtain the opaque thick liquid of khaki color.Utilize gas chromatographic detection wherein Tegin 55G productive rate, can show that its optimal conditions is: select glycerol or tetramethylolmethane, tung oil and polyvalent alcohol mol ratio are 1:2 or 1:3, and catalyzer is NaOH, KOH or Ca (OH)
2, consumption is 1 ~ 2%, temperature of reaction 200 DEG C, and the reaction times, 2h was advisable, and now Tegin 55G productive rate can be stabilized in more than 50%.
Table 1 tung oil alcoholysis reaction condition and Tegin 55G productive rate
Embodiment 26 ~ 41
For tung oil tetramethylolmethane alcoholysis product.The maleic anhydride and the stopper (Resorcinol/para benzoquinone/BHT) that add calculated amount is continued in 250mL tetra-neck flask, as shown in table 2.Heat up and start stir, allow maleic anhydride dissolve and and alcoholysis product fully mix.Logical nitrogen, then adds the catalyzer of calculated amount, starts reaction, keeps temperature of reaction.Yellow opaque solid resin product is obtained at the end of reaction.Utilize
1h-NMR spectrum calculates the reactivity of TOPER alcoholysis product, and can show that its optimal conditions is: tung oil and maleic anhydride mol ratio are 1:8, catalyzer is N, N-dimethyl benzylamine, consumption is 1%, and the reaction times is 5h, temperature of reaction is 100 DEG C, and the reactivity of final alcoholysis product can reach 89.7%.
The experiment condition of table 2 tung oil alcoholysis product maleation and alcoholysis product reactivity
Embodiment 42
For tung oil tetramethylolmethane acid half ester (TOPERMA).The Hydroxyethyl acrylate adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 0.5:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 1h, obtain yellow opaque thick liquid product (acid number is 223.7mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 40% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 2390mPas).
Embodiment 43
For tung oil tetramethylolmethane acid half ester (TOPERMA).The Hydroxyethyl acrylate adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 1:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 1h, obtain yellow opaque thick liquid product (acid number is 219.5mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 40% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 2630mPas).
Embodiment 44
For tung oil tetramethylolmethane acid half ester (TOPERMA).The Hydroxyethyl acrylate adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 1.5:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 1h, obtain yellow opaque thick liquid product (acid number is 216.8mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 40% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 1770mPas).
Embodiment 45
For tung oil tetramethylolmethane acid half ester (TOPERMA).The Hydroxyethyl acrylate adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 2:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 1h, obtain yellow opaque thick liquid product (acid number is 212.4mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 40% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 1370mPas).
Embodiment 46
For tung oil tetramethylolmethane acid half ester (TOPERMA).The Hydroxyethyl acrylate adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 5:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 1h, obtain yellow opaque thick liquid product (acid number is 210.1mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 40% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 990mPas).
Embodiment 47
For tung oil tetramethylolmethane acid half ester (TOPERMA).The Hydroxyethyl acrylate adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 1.5:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 5h, obtain yellow opaque thick liquid product (acid number is 211.3mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 40% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 880mPas).
Embodiment 48
For tung oil tetramethylolmethane acid half ester (TOPERMA).The Hydroxyethyl acrylate adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 1.5:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 10h, obtain yellow opaque thick liquid product (acid number is 213.2mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 40% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains brown translucent liquid resin (viscosity is 910mPas).
Embodiment 49
For tung oil tetramethylolmethane acid half ester (TOPERMA).The hydroxyethyl methylacrylate adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 1.5:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 5h, obtain yellow opaque thick liquid product (acid number is 215.4mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 40% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 1290mPas).
Embodiment 50
For tung oil tetramethylolmethane acid half ester (TOPERMA).The Propylene glycol monoacrylate adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 1.5:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 5h, obtain yellow opaque thick liquid product (acid number is 217.0mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 40% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 1450mPas).
Embodiment 51
For tung oil tetramethylolmethane acid half ester (TOPERMA).The Rocryl 410 adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 1.5:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 5h, obtain yellow opaque thick liquid product (acid number is 217.5mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 40% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 1530mPas).
Embodiment 52
For tung oil tetramethylolmethane acid half ester (TOPERMA).The hy-droxybutyl adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 1.5:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 5h, obtain yellow opaque thick liquid product (acid number is 217.3mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 40% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 1580mPas).
Embodiment 53
For tung oil tetramethylolmethane acid half ester (TOPERMA).The methacrylate adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 1.5:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 5h, obtain yellow opaque thick liquid product (acid number is 217.9mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 40% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 1710mPas).
Embodiment 54
For tung oil tetramethylolmethane acid half ester (TOPERMA).The vinylcarbinol adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 1.5:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 5h, obtain yellow opaque thick liquid product (acid number is 210.7mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 40% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 850mPas).
Embodiment 55
For tung oil tetramethylolmethane acid half ester (TOPERMA).The methylallyl alcohol adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 1.5:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 5h, obtain yellow opaque thick liquid product (acid number is 214.1mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 40% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 1070mPas).
Embodiment 56
For tung oil tetramethylolmethane acid half ester (TOPERMA).The Hydroxyethyl acrylate adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 1.5:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 5h, obtain yellow opaque thick liquid product (acid number is 211.8mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 30% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 1570mPas).
Embodiment 57
For tung oil tetramethylolmethane acid half ester (TOPERMA).The Hydroxyethyl acrylate adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 1.5:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 5h, obtain yellow opaque thick liquid product (acid number is 210.9mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 50% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 650mPas).
Embodiment 58
For tung oil tetramethylolmethane acid half ester (TOPERMA).The Hydroxyethyl acrylate adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 1.5:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 5h, obtain yellow opaque thick liquid product (acid number is 211.6mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 60% and the Resorcinol of 0.1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 370mPas).
Embodiment 59
For tung oil tetramethylolmethane acid half ester (TOPERMA).The Hydroxyethyl acrylate adding calculated amount is continued in above-mentioned TOPERMA product, the mol ratio making itself and tung oil is 1.5:1, keep the condition such as catalyzer, temperature of reaction of synthesis TOPERMA to continue reaction 5h, obtain yellow opaque thick liquid product (acid number is 210.9mgKOH/g).At 80 ~ 100 DEG C, add total resin weight is the vinylbenzene of 40% and the Resorcinol of 1% vinylbenzene weight, stirs 1h, obtains reddish-brown translucent liquid resin (viscosity is 870mPas).
Embodiment 60 ~ 63
Take 100g embodiment 47 and 56 ~ 58 resin, add the peroxidized t-butyl perbenzoate of 2% total resin weight, stir 30min, and degassed process, finally pour film forming in self-control Teflon mould into.Utilize SANS7CMT-4304 type universal testing machine (Instrument Ltd. is newly thought carefully in Shenzhen), test its stretching, bending property by GB/T2567-2008 " casting resin method for testing performance ".Elongation test speed is 5.0mm/min, and test sample is dumbbell shape, and its length is 200mm, and narrower middle portion is of a size of 50 × 10 × 4mm
3.Crooked test speed is 10mm/min, and test sample is rectangle, and it is of a size of 100 × 15 × 4mm
3.Second-order transition temperature is got (being determined by the peak value of dissipation factor) by thermomechanical analyzer.Its index visible meets the moulding compound requirement of general general UPR substantially.
The main performance index of table 3 embodiment 47 and 53 – 56 resin sample
Embodiment 64
For embodiment 47 resin.Get resin 100g, then add the Resorcinol of 0.1% total resin weight, then add 4g magnesium oxide, stir.NDJ-8S type rotary viscosity is utilized to measure its viscosity.Resin initial viscosity is 880mPas, and after 48h, its viscosity is more than 2 × 10
6mPas, grows beyond 2000 times.Therefore, the unsaturated ester resin thickening property altogether of this tung oil base is good, can be used for making moulding compound.
The invention is not restricted to above-described embodiment, all can implement described in content of the present invention and there is described good result.
Claims (10)
1. a synthetic method for the unsaturated ester resin altogether of moulding compound tung oil base, is characterized in that preparation process is:
(1) under the effect of acid or basic catalyst, be heated to 150 ~ 250 DEG C of reaction 1 ~ 10h, make tung oil and polyvalent alcohol generation alcoholysis reaction, generation tung oil base mono-glycerides alcoholysis product, catalyst levels is 0.2 ~ 4% of tung oil and total polyol weight; Described polyvalent alcohol is at least one in dihydroxyphenyl propane alcohols, glycerol, tetramethylolmethane; The material molar ratio of described polyvalent alcohol and tung oil is 1:1 ~ 4:1;
(2) then add maleic anhydride, the material molar ratio of maleic anhydride and tung oil is 2:1 ~ 10:1, under the existence of catalyzer and stopper, continues heating 50 ~ 200 DEG C, and reaction 1 ~ 10h generates tung oil base acid half ester; Stopper is at least one in Resorcinol, para benzoquinone, BHT, and consumption is 0.1 ~ 1% of raw material gross weight;
(3) propene compound is added again, described propene compound is at least one in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, hy-droxybutyl, methacrylate, vinylcarbinol or methacrylic alcohols, the material molar ratio of propene compound and tung oil is 0.5:1 ~ 5:1, continue heating 50 ~ 200 DEG C, reaction 1 ~ 10h, generates the unsaturated ester altogether of propenyl-maleinization tung oil base; Be cooled to 80 ~ 100 DEG C after reaction terminates, add the vinylbenzene being dissolved with stopper and dilute, described vinylbenzene add-on is 30 ~ 60% of the unsaturated ester weight altogether of tung oil base, and stopper is 0.1 ~ 1% of vinylbenzene weight, is uniformly dispersed and obtains end product.
2. synthetic method according to claim 1, is characterized in that described in step (1), basic catalyst is sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium ethylate, potassium ethylate, sodium methylate, potassium methylate or caoxalate; An acidic catalyst is sulfuric acid, hydrochloric acid, nitric acid or sulfonic acid.
3. synthetic method according to claim 1, it is characterized in that the Heating temperature described in step (1) is 200 DEG C, the reaction times is 2h; Described polyvalent alcohol and the material molar ratio of tung oil are 2:1 or 3:1.
4. preparation method according to claim 1, is characterized in that the material molar ratio of the maleic anhydride described in step (2) and tung oil is 8:1; Described Heating temperature 100 DEG C, the reaction times is 5h.
5. preparation method according to claim 1, it is characterized in that described in step (2), catalyzer is sulfuric acid, tosic acid, sodium hydroxide, N, N-dimethyl benzylamine, triphenylphosphine or Methylimidazole, consumption is 0.2 ~ 4% of tung oil alcoholysis product and maleic anhydride gross weight.
6. preparation method according to claim 1, is characterized in that the material molar ratio of the propene compound described in step (3) and tung oil is 1.5:1.
7. preparation method according to claim 1, it is characterized in that the Heating temperature described in step (3) is 100 DEG C, the reaction times is 5h.
8. preparation method according to claim 1, it is characterized in that the vinylbenzene add-on described in step (3) is 40% of the unsaturated ester weight altogether of tung oil base, stopper is 0.1% of vinylbenzene weight.
9. the unsaturated ester resin altogether of the tung oil base for preparing of the arbitrary described method of claim 1 ~ 8.
10. the application of the unsaturated ester resin altogether of tung oil base described in claim 9 in preparation sheet/Bulk Molding Compound.
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