CN112812276A - Preparation method of rosin modified terpene phenol resin - Google Patents
Preparation method of rosin modified terpene phenol resin Download PDFInfo
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- CN112812276A CN112812276A CN202110072181.9A CN202110072181A CN112812276A CN 112812276 A CN112812276 A CN 112812276A CN 202110072181 A CN202110072181 A CN 202110072181A CN 112812276 A CN112812276 A CN 112812276A
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- Prior art keywords
- rosin
- phenol resin
- modified terpene
- terpene phenol
- acid
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- 150000003505 terpenes Chemical class 0.000 title claims abstract description 110
- 235000007586 terpenes Nutrition 0.000 title claims abstract description 110
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 90
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 87
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 239000002131 composite material Substances 0.000 claims abstract description 60
- 239000002253 acid Substances 0.000 claims abstract description 42
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000002378 acidificating effect Effects 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000010992 reflux Methods 0.000 claims abstract description 18
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 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 12
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 10
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 claims description 10
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 9
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 9
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002023 wood Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229930006737 car-3-ene Natural products 0.000 claims description 6
- BQOFWKZOCNGFEC-UHFFFAOYSA-N carene Chemical compound C1C(C)=CCC2C(C)(C)C12 BQOFWKZOCNGFEC-UHFFFAOYSA-N 0.000 claims description 6
- 229930007796 carene Natural products 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims description 5
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 claims description 5
- 229930006739 camphene Natural products 0.000 claims description 5
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 claims description 5
- 235000001510 limonene Nutrition 0.000 claims description 5
- 229940087305 limonene Drugs 0.000 claims description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 5
- 239000003784 tall oil Substances 0.000 claims description 5
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 4
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 claims description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 claims description 3
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 claims description 3
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 claims description 3
- 229930006722 beta-pinene Natural products 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003377 acid catalyst Substances 0.000 abstract description 3
- 239000012855 volatile organic compound Substances 0.000 abstract 2
- 239000010865 sewage Substances 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 29
- 229920005989 resin Polymers 0.000 description 29
- 239000000126 substance Substances 0.000 description 10
- 239000004831 Hot glue Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 229940098779 methanesulfonic acid Drugs 0.000 description 4
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 4
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 3
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006114 decarboxylation reaction Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 1
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical group C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010500 citrus oil Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000003712 decolorant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000008096 xylene Substances 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1422—Side-chains containing oxygen containing OH groups
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3323—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other monocyclic systems
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/72—Derivatisation
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/75—Reaction of polymer building blocks for the formation of block-copolymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A preparation method of rosin modified terpene phenol resin comprises the following steps: 1) firstly, heating, melting and uniformly mixing phenol and an acidic composite catalyst to obtain a phenol-acidic composite catalyst mixture; heating terpene to 80-150 ℃, then dropwise adding a phenol-acid composite catalyst mixture into the terpene, and stirring; finally adding rosin, heating and refluxing for reaction; 2) after the reaction is finished, adding a neutralizing agent to neutralize the acidic composite catalyst, then continuing heating up and refluxing for reaction, and finally vacuumizing to remove residual phenol, rosin light fraction and terpene oligomer until the test index meets the requirement; 3) cooling, adding an antioxidant, uniformly stirring and discharging to obtain the rosin modified terpene phenol resin. The rosin modified terpene phenol resin is synthesized by adopting the composite protonic acid catalyst under the solvent-free condition, has the characteristics of high temperature resistance, good flexibility and low-temperature tackifying effect, has less sewage and VOC (volatile organic compounds) emission, and is environment-friendly.
Description
Technical Field
The invention relates to the field of chemical products, in particular to a preparation method of rosin modified terpene phenol resin.
Background
The terpene-phenol resin is a phenol modified terpene resin and is obtained by copolycondensating terpene and phenol under the condition of a catalyst. Wherein the terpene is unsaturated cyclic C derived from turpentine, sulfate papermaking process and citrus oil10Hydrocarbons, a natural renewable resource. The terpene-phenol resin has good compatibility with various matrix resins, is an excellent tackifying resin of acrylic resin, styrene-butadiene rubber, natural rubber, chloroprene rubber, SIS (styrene-isoprene-styrene block copolymer) and SBS (styrene-butadiene-styrene block copolymer), and can provide ductility and flexibility for manufacturing hot melt adhesives and coatings. The preparation of terpene phenol resin generally adopts Friedel-crafts catalysts such as boron trifluoride and aluminum trichloride and protonic acid catalysts such as sulfuric acid and benzenesulfonic acid; generally, a cold polymerization process is adopted, and benzene solvents such as toluene, xylene and the like are often used in the preparation process. And after the reaction is finished, adding a catalyst neutralizer, washing with water, separating a water layer from an organic layer, distilling the organic layer at a high temperature, and removing the solvent and low molecular weight substances to obtain the tackifying resin. In addition, volatile and toxic organic solvents such as dimethylbenzene are used, which is not beneficial to controlling the VOC content in resin products.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of rosin modified terpene phenol resin with different ring and ball softening points, the rosin modified terpene phenol resin has the characteristics of high temperature resistance and good low-temperature adhesion, and the preparation method adopts a composite protonic acid catalyst, does not need to use a solvent and neutralize and wash water, does not produce a large amount of waste water, and can reduce environmental pollution.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of rosin modified terpene phenol resin comprises the following steps:
1) firstly, heating, melting and uniformly mixing phenol and an acidic composite catalyst to obtain a phenol-acidic composite catalyst mixture; heating terpene to 80-150 ℃, then dropwise adding a phenol-acid composite catalyst mixture into the terpene, and stirring; finally adding rosin, heating and refluxing for reaction;
2) after the reaction is finished, adding a neutralizing agent to neutralize the acidic composite catalyst, then continuing heating up and refluxing for reaction, and finally vacuumizing to remove residual phenol, rosin light fraction and terpene oligomer until the test index meets the requirement;
3) cooling, adding an antioxidant, uniformly stirring and discharging to obtain the rosin modified terpene phenol resin.
The acidic composite catalyst comprises organic protonic acid and inorganic protonic acid.
The inorganic protonic acid comprises sulfuric acid, phosphoric acid and hypophosphorous acid; the organic protonic acid comprises benzene sulfonic acid, p-methyl benzene sulfonic acid, methyl sulfonic acid and dodecyl benzene sulfonic acid.
The terpene comprises at least one of alpha-pinene, beta-pinene, limonene, dipentene, carene, terpinolene and camphene.
The rosin comprises at least one of gum rosin, wood rosin and tall oil rosin; the neutralizer comprises magnesium oxide, zinc oxide and calcium oxide.
The weight ratio of the phenol to the terpene is 1.5-0.3; the weight ratio of the rosin to the terpene is 0.6-2.0.
The weight percentage of the acidic composite catalyst and the terpene is 0.1-2%.
In the step 1), the heating and melting temperature is 60-90 ℃; the temperature of the heating reflux is 120-160 ℃, and the time is 5-10 h.
In the step 2), the temperature of the heating reflux is 240-280 ℃, and the time is 4-8 h; in step 3), the temperature is reduced to below 210 ℃, and an antioxidant is added.
The rosin modified terpene phenol resin prepared by the preparation method has a ring-ball softening point of 95-150 ℃, an acid value of 15-50 and a weight average molecular weight of 800-1300.
Rosin is an important natural product in China and is a viable resource. After the terpene-phenol resin is modified by rosin, rosin acid groups are introduced into the terpene-phenol polymer, so that the high temperature resistance, the cohesion and the compatibility of the resin can be improved, and the application of the resin in the fields of adhesives, printing ink and rubber can be widened.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the invention uses rosin in modified terpene phenol resin by chemical method, under the condition of acid composite catalyst, rosin and earlier stage terpene-phenol copolymer are further reacted and polycondensed, after the polycondensation reaction is terminated by neutralizing acid composite catalyst, the temperature is further raised to make terpene-phenol-rosin copolymer produce intermolecular esterification reaction, so that the acid value can be reduced, and the ageing resistance of resin can be raised. The rosin modified terpene phenol resin prepared by the method of the invention introduces abietic acid with a tricyclic condensed ring structure into the terpene phenol resin, increases the rigidity and polarity of the resin, and can improve the adhesive force, cohesive force, heat resistance, aging resistance and low-temperature adhesive property of the adhesive.
The rosin modified terpene phenol resin prepared by the invention has important application in preparing hot melt adhesive. The rosin modified terpene phenol resin has high temperature resistance, good flexibility and low-temperature tackifying effect, the polarity and softening point of the resin can be adjusted according to the using amounts of rosin and phenol, the rosin modified terpene phenol resin has good compatibility with elastomers such as EVA elastomers, natural rubber, chloroprene rubber, SIS rubber and SBS rubber, the rosin modified terpene phenol resin can be used as tackifying resin of an adhesive, and preferably used as pressure-sensitive hot melt adhesive and hot melt adhesive tackifying resin with high temperature resistance, good flexibility and low-temperature tackifying effect, in addition, the polarity and glossiness of the resin can be adjusted by adjusting the weight ratio of phenol to terpene and the weight ratio of rosin to terpene, and the resin is applied to the field of ink.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention clearer and more obvious, the present invention is further described in detail below with reference to the following embodiments.
The invention relates to a preparation method of rosin modified terpene phenol resin, which comprises the following steps:
1) firstly, heating, melting and uniformly mixing phenol and an acidic composite catalyst at 60-90 ℃ to obtain a phenol-acidic composite catalyst mixture; heating terpene to 80-150 ℃, then dropwise adding a phenol-acid composite catalyst mixture into the terpene, and stirring to synthesize a polycondensation product of phenol and terpene; finally, adding the crushed rosin in batches, heating to 120-160 ℃, and carrying out reflux reaction for 5-10 h to further polymerize the rosin and the terpene phenol polycondensation product;
2) after the reaction is finished, adding a neutralizing agent to neutralize the acidic composite catalyst to prevent decarboxylation and decomposition of the resin at high temperature, and then continuously refluxing for 4-8 h at 240-280 ℃ to perform esterification reaction and reduce the acid value; finally, vacuumizing to remove residual phenol, rosin light fraction and terpene oligomer until the test index meets the requirement; if light-colored resin is needed, a thiophenol decolorant (such as 4, 4' -thiobis (6-tert-butyl-3-methylphenol)) can be added after the acid composite catalyst is neutralized for light-colored treatment;
3) cooling to below 210 ℃, adding an antioxidant, uniformly stirring and discharging to obtain the rosin modified terpene phenol resin.
The terpene is at least one of alpha-pinene, beta-pinene, limonene, dipentene, carene, terpinolene and camphene; in a more preferred embodiment, the terpene is at least one of α -pinene, limonene, dipentene, carene, terpinolene, camphene; in a most preferred embodiment, the terpene is at least one of limonene, dipentene, carene, terpinolene, camphene. The terpene raw materials of the invention all adopt terpene clear oil prepared by the company.
The acidic composite catalyst is composed of at least two of sulfuric acid, phosphoric acid, hypophosphorous acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid and dodecylbenzenesulfonic acid. The acidic composite catalyst is mainly used for catalyzing the condensation polymerization of terpene, phenol and rosin, and improving the reaction efficiency. The catalytic efficiency of sulfuric acid and phosphoric acid is high, but equipment is easy to corrode, rosin decarboxylation is easy to cause, and side reactions are increased; the hypophosphorous acid has medium catalytic efficiency and certain decolorizing effect. Organic protonic acids such as benzenesulfonic acid, p-toluenesulfonic acid and the like have medium catalytic efficiency, but the boiling point of the catalyst is low, and the reaction temperature needs to be controlled to be low, so that the reaction time is long, and the production of light-colored resin is not facilitated. Through a great deal of research, the invention discovers that the use of the catalyst compounded with the organic protonic acid and the inorganic protonic acid can improve the reaction temperature, shorten the reaction time, improve the polycondensation reaction efficiency of the terpene, the phenol and the rosin and obtain the light-colored resin.
The weight ratio of the phenol to the terpene is 1.5-0.3; in a more preferred embodiment, the weight ratio of phenol to terpene is 1.0 to 0.3; in a most preferred embodiment, the weight ratio of phenol to terpene is from 0.8 to 0.4. The amount of phenol directly affects the early polycondensation reaction and the late esterification reaction. As the amount of phenol increases, the softening point increases and the polarity of the resin increases. However, if the amount of phenol is too large, the transparency of the resin is lowered, and the application of the resin in hot melt adhesives is affected.
The weight ratio of the acidic composite catalyst to the terpene is 0.1-2%; in a particularly preferred embodiment, the weight ratio of the acidic composite catalyst to the terpene is from 0.2% to 1.5%. When the dosage of the acidic composite catalyst is less than 0.1%, the catalytic efficiency is low, and the yield of the obtained product is low; with the increase of the dosage of the acidic composite catalyst, the product yield is increased and the softening point is increased; when the dosage of the acidic composite catalyst is more than 2 percent, side reaction is increased, rosin decarboxylation occurs, the resin yield is reduced, and the softening point is reduced.
The rosin is at least one of gum rosin, wood rosin and tall oil rosin. Suitable rosins may be of various origins, gum rosins obtained by distillation of rosin; wood rosin extracted from pine wood chips; tall oil rosin, a by-product of the sulfate papermaking process. The rosin is mainly C20The tricyclic condensed ring monocarboxylic acid (represented by abietic acid and pimaric acid) contains a plurality of double bonds in the molecule, so that under the action of an acidic composite catalyst, rosin can be subjected to polycondensation reaction with a terpene-phenol copolymer at a low temperature, part of rosin can also be directly subjected to alkylation reaction with phenol, and after the acidic composite catalyst is neutralized, the temperature is increased, esterification reaction can be further performed, the acid value is reduced, and the aging resistance of the resin is improved.
The weight ratio of the rosin to the terpene is 0.6-2.0; in a particularly preferred embodiment, the weight ratio of rosin to terpene is from 0.8 to 1.5; the use amount of the rosin is increased, so that the molecular weight of the resin can be increased, and the softening point of the resin can be increased.
The resin prepared by the method has a ring-ball softening point of 95-150 ℃, an acid value of 15-50 and a weight average molecular weight of 800-1300.
Example 1
In an embodiment of the method for preparing rosin modified terpene phenol resin of the present invention, the method of this embodiment comprises the following steps:
(1) 127g of phenol and 0.43g of an acidic composite catalyst (50% of sulfuric acid and 50% of benzenesulfonic acid) were heated, melted and mixed uniformly at 85 ℃ to obtain a phenol-acidic composite catalyst mixture.
(2) 425g of terpene naphtha TO1 (produced by Zhongkun chemical company and mainly comprising dipentene, carene and terpinolene) was put into a four-neck flask and heated TO 90 ℃. The phenol-acid composite catalyst mixture is dripped at the temperature of 90 ℃ for 1 hour, and the stirring is continued for 1 hour after the addition.
(3) 361g of crushed first-class gum rosin is added in batches, the temperature is raised to 120 ℃, and the reflux reaction is carried out for 8 hours.
(4) Adding 0.6g of magnesium oxide serving as a neutralizing agent, stirring for 30min, and neutralizing the acidic composite catalyst.
(5) Heating to 265 ℃ and keeping the temperature for reaction for 4 h. And starting a vacuum pump, and vacuumizing for 3 hours until the test index meets the target requirement.
(6) And cooling to 210 ℃, adding the antioxidants 1010 and 168, uniformly stirring and discharging to obtain the rosin modified terpene phenol resin.
The rosin-modified terpene phenol resin obtained in this example, as measured by the ring and ball method, had a softening point of 98.0 ℃ and an acid value of 35.8mg KOH/g.
Example 2
In an embodiment of the method for preparing rosin modified terpene phenol resin of the present invention, the method of this embodiment comprises the following steps:
(1) 386g of phenol and 2.8g of composite catalyst (50 percent of phosphoric acid, 20 percent of benzenesulfonic acid and 30 percent of dodecylbenzenesulfonic acid) are heated, melted and mixed uniformly at 65 ℃ to obtain a phenol-acid composite catalyst mixture.
(2) 550g of terpene clear oil TO2 (produced by Zhongkun chemical company, and mainly composed of dipentene and terpinolene) was put into a four-neck flask, and the temperature was raised TO 130 ℃. Dripping the mixture of the phenol-acid composite catalyst for 1 hour at the temperature of 130 ℃, and continuing stirring for 1 hour after the addition.
(3) 385g of crushed primary wood rosin is added in batches, the temperature is raised to 140 ℃, and the reflux reaction is carried out for 6 hours.
(4) Adding 4.5g of zinc oxide as a neutralizing agent, stirring for 30min, and neutralizing the acidic composite catalyst.
(5) Heating to 260 ℃ and keeping the temperature for reaction for 6 h. And starting a vacuum pump, and vacuumizing for 4 hours until the test index meets the target requirement.
(6) And cooling to 210 ℃, adding the antioxidants 1010 and 168, uniformly stirring and discharging to obtain the rosin modified terpene phenol resin.
The rosin-modified terpene phenol resin obtained in this example, as measured by the ring and ball method, had a softening point of 127.5 ℃ and an acid value of 46.9mg KOH/g.
Example 3
In an embodiment of the method for preparing rosin modified terpene phenol resin of the present invention, the method of this embodiment comprises the following steps:
(1) 420g of phenol and 6.3g of a composite catalyst (50% of hypophosphorous acid, 30% of benzenesulfonic acid and 20% of methanesulfonic acid) were heated, melted and mixed uniformly at 80 ℃ to obtain a phenol-acidic composite catalyst mixture.
(2) 525g of terpene naphtha TO1 (produced by Zhongkun chemical company, main components of dipentene and terpinolene) was put into a four-neck flask, and the temperature was raised TO 110 ℃. Dripping the phenol-acid composite catalyst mixture for 2 hours at the temperature of 110 ℃, and continuing stirring for 1 hour after the addition is finished.
(3) 367g of crushed first-grade wood rosin is added in batches, the temperature is raised to 130 ℃, and the reflux reaction is carried out for 8 hours.
(4) Adding 8.2g of calcium oxide serving as a neutralizing agent, stirring for 30min, and neutralizing the acidic composite catalyst.
(5) Heating to 270 ℃ and preserving the temperature for reaction for 6 h. And starting a vacuum pump, and vacuumizing for 3 hours until the test index meets the target requirement.
(6) And cooling to 210 ℃, adding the antioxidants 1010 and 168, uniformly stirring and discharging to obtain the rosin modified terpene phenol resin.
The rosin-modified terpene phenol resin obtained in this example, as measured by the ring and ball method, had a softening point of 123.0 ℃ and an acid value of 18.7mg KOH/g.
Example 4
In an embodiment of the method for preparing rosin modified terpene phenol resin of the present invention, the method of this embodiment comprises the following steps:
(1) 384g phenol and 8.7g composite catalyst (50% sulfuric acid, 25% p-toluenesulfonic acid and 25% methanesulfonic acid) were heated, melted and mixed uniformly at 70 ℃ to obtain a phenol-acid composite catalyst mixture.
(2) 480g of terpene naphtha TO2 (produced by Zhongkun chemical company, and the main components of which are dipentene and terpinolene) are added into a four-neck flask, and the temperature is raised TO 130 ℃. Dripping the phenol-acid composite catalyst mixture for 2 hours at the temperature of 130 ℃, and continuing stirring for 1 hour after the addition is finished.
(3) 480g of crushed first-grade gum rosin is added in batches, the temperature is raised to 150 ℃, and the reflux reaction is carried out for 6 hours.
(4) Adding magnesium oxide as neutralizer 12.0g, stirring for 30min, and neutralizing the acidic composite catalyst.
(5) Heating to 275 deg.c and maintaining the temperature for reaction for 5 hr. And starting a vacuum pump, and vacuumizing for 4 hours until the test index meets the target requirement.
(6) And cooling to 210 ℃, adding an antioxidant DTBHQ, uniformly stirring and discharging to obtain the rosin modified terpene phenol resin.
The rosin-modified terpene phenol resin obtained in this example had a softening point of 147.5 ℃ and an acid value of 42.7mg KOH/g, as measured by the ring and ball method.
Example 5
In an embodiment of the method for preparing rosin modified terpene phenol resin of the present invention, the method of this embodiment comprises the following steps:
(1) 306g of phenol and 9.2g of a composite catalyst (50% of phosphoric acid, 20% of p-toluenesulfonic acid and 30% of methanesulfonic acid) were heated, melted and mixed uniformly at 87 ℃ to obtain a phenol-acidic composite catalyst mixture.
(2) 510g of terpene varnish TO2 (manufactured by Zhongkun chemical company, and mainly containing dipentene and terpinolene) was put into a four-neck flask, and the temperature was raised TO 140 ℃. Dripping the phenol-acid composite catalyst mixture for 2 hours at the temperature of 140 ℃, and continuing stirring for 1 hour after the addition is finished.
(3) 357g of crushed tall oil rosin is added in batches, the temperature is raised to 150 ℃, and the reflux reaction is carried out for 6 hours.
(4) Adding 12.8g of magnesium oxide serving as a neutralizing agent, stirring for 30min, and neutralizing the acidic composite catalyst.
(5) Heating to 255 ℃ and keeping the temperature for reaction for 7 h. And starting a vacuum pump, and vacuumizing for 4 hours until the test index meets the target requirement.
(6) And cooling to 210 ℃, adding the antioxidants 1010 and 168, uniformly stirring and discharging to obtain the rosin modified terpene phenol resin.
The rosin-modified terpene phenol resin obtained in this example had a softening point of 113.5 ℃ and an acid value of 21.9mg KOH/g, as measured by the ring and ball method.
Example 6
In an embodiment of the method for preparing rosin modified terpene phenol resin of the present invention, the method of this embodiment comprises the following steps:
(1) 386g of phenol and 5.9g of composite catalyst (30 percent of phosphoric acid, 40 percent of p-toluenesulfonic acid and 30 percent of benzenesulfonic acid) are heated, melted and mixed uniformly at 80 ℃ to obtain a phenol-acid composite catalyst mixture.
(2) 392g of terpene naphtha TO1 (produced by Zhongkun chemical company, main components of dipentene and terpinolene) was put into a four-neck flask, and the temperature was raised TO 120 ℃. Dripping the phenol-acid composite catalyst mixture for 3 hours at the temperature of 120 ℃, and continuing stirring for 1 hour after the addition is finished.
(3) 429g of crushed primary wood rosin is added in batches, the temperature is raised to 150 ℃, and the reflux reaction is carried out for 6 hours.
(4) Adding 8.19g of magnesium oxide serving as a neutralizing agent, stirring for 30min, and neutralizing the acidic composite catalyst.
(5) The temperature is increased to 275 ℃ and the reaction is kept for 6 h. And starting a vacuum pump, and vacuumizing for 3 hours until the test index meets the target requirement.
(6) And cooling to 210 ℃, adding the antioxidants 1010 and 168, uniformly stirring and discharging to obtain the rosin modified terpene phenol resin.
The rosin-modified terpene phenol resin obtained in this example had a softening point of 145.5 ℃ and an acid value of 27.4mg KOH/g, as measured by the ring and ball method.
The rosin modified terpene phenol resin prepared by the invention has important application in preparing hot melt adhesive. The rosin modified terpene phenol resin has high temperature resistance, good flexibility and low-temperature tackifying effect, can adjust the polarity and softening point of the resin according to the dosage of rosin and phenol, has good compatibility with elastomers such as EVA elastomers, SIS and SBS, and can be better used for preparing pressure-sensitive hot melt adhesive and hot melt adhesive.
The invention uses rosin in modified terpene phenol resin by chemical method, under the condition of acid composite catalyst, rosin and earlier stage terpene-phenol copolymer are further reacted and polycondensed, after the polycondensation reaction is terminated by neutralizing acid composite catalyst, the temperature is further raised to make terpene-phenol-rosin copolymer undergo intramolecular esterification reaction, so that the acid value can be reduced, and the ageing resistance of resin can be raised. The rosin modified terpene phenol resin prepared by the method of the invention introduces abietic acid with a tricyclic condensed ring structure into the terpene phenol resin, increases the rigidity and polarity of the resin, and can improve the adhesive force, cohesive force, heat resistance, aging resistance and low-temperature adhesive property of the adhesive.
Claims (10)
1. The preparation method of the rosin modified terpene phenol resin is characterized by comprising the following steps:
1) firstly, heating, melting and uniformly mixing phenol and an acidic composite catalyst to obtain a phenol-acidic composite catalyst mixture; heating terpene to 80-150 ℃, then dropwise adding a phenol-acid composite catalyst mixture into the terpene, and stirring; finally adding rosin, heating and refluxing for reaction;
2) after the reaction is finished, adding a neutralizing agent to neutralize the acidic composite catalyst, then continuing heating up and refluxing for reaction, and finally vacuumizing to remove residual phenol, rosin light fraction and terpene oligomer until the test index meets the requirement;
3) cooling, adding an antioxidant, uniformly stirring and discharging to obtain the rosin modified terpene phenol resin.
2. The method for preparing a rosin-modified terpene phenol resin according to claim 1, wherein the rosin-modified terpene phenol resin comprises: the acidic composite catalyst comprises organic protonic acid and inorganic protonic acid.
3. The method for producing a rosin-modified terpene phenol resin according to claim 2, wherein: the inorganic protonic acid comprises sulfuric acid, phosphoric acid and hypophosphorous acid; the organic protonic acid comprises benzene sulfonic acid, p-methyl benzene sulfonic acid, methyl sulfonic acid and dodecyl benzene sulfonic acid.
4. The method for preparing a rosin-modified terpene phenol resin according to claim 1, wherein the rosin-modified terpene phenol resin comprises: the terpene comprises at least one of alpha-pinene, beta-pinene, limonene, dipentene, carene, terpinolene and camphene.
5. The method for preparing a rosin-modified terpene phenol resin according to claim 1, wherein the rosin-modified terpene phenol resin comprises: the rosin comprises at least one of gum rosin, wood rosin and tall oil rosin; the neutralizer comprises magnesium oxide, zinc oxide and calcium oxide.
6. The method for preparing a rosin-modified terpene phenol resin according to claim 1, wherein the rosin-modified terpene phenol resin comprises: the weight ratio of the phenol to the terpene is 1.5-0.3; the weight ratio of the rosin to the terpene is 0.6-2.0.
7. The method for preparing a rosin-modified terpene phenol resin according to claim 1, wherein the rosin-modified terpene phenol resin comprises: the weight percentage of the acidic composite catalyst and the terpene is 0.1-2%.
8. The method for preparing a rosin-modified terpene phenol resin according to claim 1, wherein the rosin-modified terpene phenol resin comprises: in the step 1), the heating and melting temperature is 60-90 ℃; the temperature of the heating reflux is 120-160 ℃, and the time is 5-10 h.
9. The method for preparing a rosin-modified terpene phenol resin according to claim 1, wherein the rosin-modified terpene phenol resin comprises: in the step 2), the temperature of the heating reflux is 240-280 ℃, and the time is 4-8 h; in step 3), the temperature is reduced to below 210 ℃, and an antioxidant is added.
10. The rosin-modified terpene phenol resin produced by the production method according to any one of claims 1 to 9, characterized in that: the ring-ball softening point of the rosin modified terpene phenol resin is 95-150 ℃, the acid value is 15-50, and the weight average molecular weight is 800-1300.
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| CN104559795A (en) * | 2014-12-24 | 2015-04-29 | 广西科茂林化有限公司 | High-temperature-resistant rosin tackifying resin and preparation method thereof |
| CN110003446A (en) * | 2019-03-20 | 2019-07-12 | 江西金安林产实业有限公司 | A kind of light color and high softening-point terpene phenol resin and the preparation method and application thereof |
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| US3198760A (en) * | 1961-08-15 | 1965-08-03 | Tenneco Chem | Polychloroprene stabilized with a phenol-terpene resin and a metal resinate and process for preparation |
| CN1668717A (en) * | 2002-05-13 | 2005-09-14 | 阿利桑那化学公司 | Phenolic-modified rosin terpene resin |
| CN104559795A (en) * | 2014-12-24 | 2015-04-29 | 广西科茂林化有限公司 | High-temperature-resistant rosin tackifying resin and preparation method thereof |
| CN110003446A (en) * | 2019-03-20 | 2019-07-12 | 江西金安林产实业有限公司 | A kind of light color and high softening-point terpene phenol resin and the preparation method and application thereof |
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Application publication date: 20210518 |