CN102718934A - Cashew nut shell oil modified resorcinol bonding resin and preparation method thereof - Google Patents
Cashew nut shell oil modified resorcinol bonding resin and preparation method thereof Download PDFInfo
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- CN102718934A CN102718934A CN2012101956564A CN201210195656A CN102718934A CN 102718934 A CN102718934 A CN 102718934A CN 2012101956564 A CN2012101956564 A CN 2012101956564A CN 201210195656 A CN201210195656 A CN 201210195656A CN 102718934 A CN102718934 A CN 102718934A
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Abstract
The invention provides a cashew nut shell oil modified resorcinol bonding resin and a preparation method thereof. The preparation method mainly includes the steps: melting resorcinol at the temperature of 120-130 DEG C; preparing resorcinol-aldehyde oligomer under the action of acid catalysts and then adding cashew nut shell oil into the resorcinol-aldehyde oligomer; increasing the temperature to reach 150-180 DEG C; performing reaction for 1-2 hours; performing reduced pressure distillation in vacuum ranging from -0.08MPa to -0.10MPa; removing water and part of free resorcinol; and adding alkali binding agents for neutralization to obtain the cashew nut shell oil modified resorcinol bonding resin. The manufacturing process of the cashew nut shell oil modified resorcinol bonding resin is simple, consumption of the resorcinol is reduced, the preparation method is more environment-friendly, and the cashew nut shell oil modified resorcinol bonding resin has a wide prospect in application to steel wire and rubber bonding.
Description
Technical field:
The present invention relates to the binder resin that rubber industry is used for the steel wire binding system, particularly a kind of cashew nut oil modified Resorcinol class binder resin and preparation method thereof.It can be used for the bonding of rubber and steel-wire carcass storeroom, and it is widely used in the rubber items such as tire, pression hose, travelling belt as the methylene receptor of binding system.
Background technology:
In the radial industry, Coppered Steel Wire mainly is in order to play enhancement as framework material.Reaching efficient enhancing must make strongthener be adhered on the rubber tightly.When reaching optimum adhesion between rubber and the strongthener, rubber or rubber compounding just can reach suitable strength.And to reach the excellent bonds between steel wire and the rubber, use usually Resorcinol and verivate thereof and HMT (hexamethylenetetramine) or with HMMM (hexamethoxy methyl cyanuramide) as binding system.Wherein, Resorcinol and verivate thereof are methylene receptor, and HMT or HMMM are the methylene radical donor.In vulcanization process, methylene radical donor compound produces formaldehyde, and formaldehyde and resorcin reaction form a kind of Resorcinol-formaldehyde network structure.The formation of network structure has improved physicals, mechanical property, the bond properties of vulcanized rubber in the sulfidation.Bonding between cross-linked rubber and brass-plated steel wire cord is that the formation through bonding middle layer produces in sulfidation.The mechanism of bonding generation comprises the oxygen reaction of Salmon-Saxl between the Cu that element sulphur and brass apply in the rubber compound, has formed coarse CuxS (cuprous sulfide) layer at rubber-brass contact interface.When the CuxS layer reaches certain thickness, can reach good bond properties between rubber and the steel wire.
Natural cashew nut shell oil is a kind of abundant sustainable regenerated Biological resources; Comprise 4 kinds of staples: the cardanol about 51% (cardanol) (the two keys of band), cashew nut acid (anacardic acid), cardiac stimulant acid (cardol); 2-methyl cardiac stimulant acid (2-methyl cardol), its structural formula is following:
And treated commercial cashew nut shell oil (CNSL) is from natural cashew nut shell oil, to handle the product that obtains through decarboxylation; Basically do not contain cashew nut acid; Be mainly the cardanol more than 90%, also have the cashew nut shell oil polymkeric substance of some different polymerization degrees: the dimer and the tripolymer that mainly are cashew nut shell oil.Can find out that from the structure of its main component it is the phenolic cpd that side group has unsaturated fatty chain, can be used as the alternative materials of Resorcinol.
Present stage, because petroleum-based energy is nervous relatively, a lot of research work personnel are seeking alternative sustainable regenerated resource; With respect to the expensive price of Resorcinol, the price of cashew nut shell oil is much lower, and it is to continue reproducible resource again by the environmental protection that natural phant cashew nut shell produces; Because its proterties is liquid, boiling point is 290 ℃, and is not volatile simultaneously; Therefore substitute Resorcinol as starting material with cashew nut shell oil; Not only can reduce production costs greatly, and can reduce the existence of free Resorcinol, reduce the smoking property of resorcinol resin; Effectively reduce the toxicity in the production process, improve environmental pollution and meet the requirement of Sustainable development.In sum, study the cashew nut oil modified application of Resorcinol class binder resin in steel wire is bonding and have development space very widely, help the development of China's tyre industry.
U.S. Pat 4257926, US5030692 adopt alkylphenol (comprising cashew nut shell oil) modification Resorcinol.Because Resorcinol contains two phenolic hydroxyl group functional groups, its reactive behavior is very high, is tens times more than of phenol; Therefore under the reaction conditions that has alkylphenol to exist, Resorcinol is elder generation and aldehyde reaction always, causes free alkylphenol very many (or participating in reaction hardly); This patent is taked two step synthesis methods for this reason; Alkylphenol and aldehyde are reacted under the basic catalyst condition, form A stage resin, add Resorcinol then and make it reaction formation resin.U.S. Pat 4167540 adopts NP and Paraformaldehyde 96 under the effect of acid catalyst, to react, and adds Resorcinol then and generates resin.But the resin of this compound method is not seen and is used for the bonding purposes of steel wire.Above-mentioned two kinds of methods all are under acid or alkaline catalysts effect, earlier with alkylphenol and aldehyde reaction, add Resorcinol synthetic resins then.
The present invention proposes a kind of preparation method that the above-mentioned later stage adds the Resorcinol processing condition that improves.Adopt an acidic catalyst to make Resorcinol or alkylation Resorcinol and formolite reaction generate the small molecules performed polymer earlier; Reduce the reactive behavior in the Resorcinol structure; Reduce the reactive behavior site; Add cashew nut shell oil then,, generate the comparatively regular resin of molecular structure so that cashew nut shell oil is easy and oligopolymer generation alkylation substitution reaction and polycondensation.This method can reduce free Resorcinol content in the resin, and can make cashew nut shell oil and oligopolymer complete reaction, obtains the low cashew nut oil modified Resorcinol class binder resin of volatility and smoking property.
Summary of the invention:
The objective of the invention is to, a kind of cashew nut oil modified Resorcinol class binder resin is provided, comprise following two kinds of chemical structures:
Wherein R1, R2 can be identical, can be different, can be that H or carbonatoms are a kind of in 1～12 the alkyl, R3 can be that H, carbonatoms are 1～12 alkyl, contain a kind of in the substituent aryl in C1～6, n is 1～100 integer.
Another object of the present invention is to, a kind of preparation method of cashew nut oil modified Resorcinol class binder resin is provided, it is characterized in that comprising following steps:
With Resorcinol 120～130 ℃ of fusions; Under an acidic catalyst effect, add aldehyde backflow 15～30min, prepare Resorcinol-aldehyde oligopolymer, add cashew nut shell oil then; Be warming up to 150～180 ℃ of reactions after 1～2 hour; In-0.08MPa underpressure distillation to the-0.10MPa vacuum, remove and anhydrate and the free Resorcinol of part, obtain cashew nut oil modified Resorcinol class binder resin with the neutralizing agent neutralization.
Cashew nut oil modified Resorcinol class binder resin of the present invention can synthesize cashew nut oil modified Resorcinol class binder resin with the alkylation Resorcinol, and its preparation method is following:
Resorcinol 120～130 ℃ of fusions, under an acidic catalyst effect, is dripped alkene at 120～130 ℃; Make alkene and Resorcinol generation alkylation substitution reaction, obtain content and be mainly the mixture that a replacement Resorcinol and two replaces the Resorcinol alkylation liquids, and then drip aldehyde backflow 15～30mmin; Prepare alkylation Resorcinol-aldehyde oligopolymer; Add cashew nut shell oil at last, be warming up to 150～180 ℃ of reactions after 1～2 hour, in-0.08MPa underpressure distillation to the-0.10MPa vacuum; Remove anhydrate with the free Resorcinol of part after, obtain cashew nut oil modified Resorcinol class binder resin with the neutralizing agent neutralization.
Cashew nut shell oil of the present invention is the C15 polyphenol that side chain contains unsaturated double-bond, and the consumption of cashew nut shell oil is 0.1%～50% of Resorcinol and a cashew nut shell oil gross weight.
The aldehyde that is used for Resorcinol generation polycondensation of the present invention can be a kind of or two or more combinations of formaldehyde, acetaldehyde, butyraldehyde, furfural, isobutyric aldehyde, Paraformaldehyde 96; Preferred formaldehyde; The mol ratio of aldehyde and Resorcinol is 0.05～0.80: 1, preferred 0.5～0.75: 1.
Acid catalyst of the present invention can be a kind of or two or more combinations in tosic acid, alkyl benzene sulphonate(ABS), sulfuric acid, hydrochloric acid, oxalic acid, the thionamic acid, and the acid catalyst add-on is 0.3%～3% of a Resorcinol weight.
The alkylating alkene of Resorcinol that is used for of the present invention is unsaturated olefin or unsaturated diolefine; Be mainly vinylbenzene, alpha-methyl styrene, p-methylstyrene, diisobutylene, isooctene, Vinylstyrene, vinyl naphthalene, a di isopropenylbenzene, to a kind of or two or more combinations in the aromatic compound of di isopropenylbenzene, Vinyl toluene, Vinyl toluene; Optimization styrene; Wherein the mol ratio of Resorcinol and alkene is 1: 0.01～1: 1, preferred 1: 0.3～1: 0.8.
Neutralizing agent of the present invention is a kind of in NaOH, KOH, organic bases DBU, triethylamine, amine acetate, the trolamine, and the neutralizing agent consumption is 0～1.0g, preferred NaOH.
The prepared cashew nut oil modified Resorcinol class binder resin ME of the present invention is simple, and the Resorcinol usage quantity reduces, more environmental protection, and being applied to has long-range prospect to the bond properties that improves steel wire and rubber in the steel wire adhesive rubber prescription.
Embodiment:
Principle of the present invention is: adopt alkylated reaction; It is exactly not gram reaction; Promptly under the katalysis of an acidic catalyst; Two keys of alkene are opened and Resorcinol generation addition reaction, and two keys of cashew nut shell oil (cardanol) side chain are opened and Resorcinol-aldehyde oligopolymer generation addition reaction, generate cashew nut oil modified Resorcinol class binder resin.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.
Embodiment 1:
In the 500ml four-hole round-bottom reaction flask of whisking appliance, TM, reflux exchanger and tap funnel is housed, add 110.1g (1mol) Resorcinol and tosic acid (PTSA) 0.55g, be heated to 120 ℃ and make mixture melt; Drip 37% formalin 46.8g (0.578mol) then; Behind the backflow 15min, add cashew nut shell oil 40g, be warming up to 160 ℃ and keep 60mmin; Underpressure distillation under-0.08MPa vacuum then; Remove anhydrate with the free Resorcinol of part after, add 50% NaOH aqueous solution 0.30g neutralization, stir the last discharging of 10min and obtain cashew nut oil modified Resorcinol class binder resin.
Embodiment 2～6; Operating procedure according to embodiment 1; Change the consumption of raw material in the building-up process, it is as shown in table 1 that synthetic cashew nut oil modified Resorcinol class binder resin (R-F-CNSL resin), the consumption of raw material and synthetic obtain the performance perameter of R-F-CNSL resin.
Synthesizing of table 1R-F-CNSL resin
Embodiment 7:
In the 500ml four-hole round-bottom reaction flask of whisking appliance, TM, reflux exchanger and tap funnel is housed; Add 110.1g (1mol) Resorcinol and the 0.28g vitriol oil (98%), be heated to 120 ℃ and make mixture melt, drip 37% formalin 54.30g (0.67mol) then; Behind the backflow 30min; Add cashew nut shell oil 60g and be warming up to 160 ℃ and keep 60mmin, then-the 0.09MPa underpressure distillation, remove anhydrate with the free Resorcinol of part after; The NaOH aqueous solution 0.48g neutralization of adding 50% is stirred the last discharging of 10min and is obtained cashew nut oil modified Resorcinol class binder resin.The softening temperature of resin is 118 ℃, free Resorcinol 9.0%.
Embodiment 8:
In the 500ml four-hole round-bottom reaction flask of whisking appliance, TM, reflux exchanger and tap funnel is housed; Add 110.1g (1mol) Resorcinol and 1.40g Witco 1298 Soft Acid, be heated to 120 ℃-130 ℃ and make mixture melt, drip 37% formalin 34.05g (0.42mol) and Paraformaldehyde 96 3g then; Behind the backflow 20min; Add cashew nut shell oil 75g and be warming up to 160 ℃ and keep 60min, then-the 0.10MPa underpressure distillation, remove anhydrate with the free Resorcinol of part after; The NaOH aqueous solution 0.34g neutralization of adding 50% is stirred the last discharging of 10min and is obtained cashew nut oil modified Resorcinol class binder resin.The softening temperature of resin is 78 ℃, free Resorcinol 14.84%.
Embodiment 9:
In the 500ml four-hole round-bottom reaction flask of whisking appliance, TM, reflux exchanger and tap funnel is housed; Add 110.1g (1mol) Resorcinol and 1.0g tosic acid and 0.30g oxalic acid, be heated to 130 ℃ and make mixture melt, drip 37% formalin 32.43g (0.40mol) and Paraformaldehyde 96 8g then; Behind the backflow 30min; Add cashew nut shell oil 50g and be warming up to 180 ℃ and keep 40min, then-the 0.10MPa underpressure distillation, remove anhydrate with the free Resorcinol of part after; Add the 0.18g triethylamine, stir the last discharging of 10min and obtain cashew nut oil modified Resorcinol class binder resin.The softening temperature of resin is 135.0 ℃, free Resorcinol 6.0%.
Embodiment 10:
In the 500ml four-hole round-bottom reaction flask of whisking appliance, TM, reflux exchanger and tap funnel is housed; Add 110.1g (1mol) Resorcinol and tosic acid (PTSA) 1.0g; Be heated to mixture melt, then 52.1g (0.64mol) vinylbenzene progressively slowly dropped in the fused Resorcinol.Dropping temperature after vinylbenzene dropwises, keeps stirring 15min at 125 ℃; Between temperature control to 100 ℃, drip 37% formalin then, dropwise backflow 15min after; Add cashew nut shell oil 9g, be warming up to 160 ℃ and keep about 60mmin, underpressure distillation under-0.08MPa vacuum; Except that anhydrating and the free Resorcinol of part, add 50% NaOH aqueous solution 0.50g neutralization then, discharging obtains cashew nut oil modified Resorcinol class binder resin behind the stirring 10min.
Embodiment 11:
In the 500ml four-hole round-bottom reaction flask of whisking appliance, TM, reflux exchanger and tap funnel is housed; Add 110.1g (1mol) Resorcinol and tosic acid (PTSA) 1.0g; Be heated to mixture melt, then 66.7g (0.5mol) vinylbenzene progressively slowly dropped in the fused Resorcinol.Dropping temperature after vinylbenzene dropwises, keeps stirring 30min at 135 ℃; Between temperature control to 120 ℃, drip 37% formalin then, dropwise backflow 15mmin after; Add cashew nut shell oil 21g, be warming up to 150 ℃ and keep about 120min, underpressure distillation under-0.10MPa vacuum; Add 50% NaOH aqueous solution 0.50g neutralization then, stir 10min after last discharging obtain cashew nut oil modified Resorcinol class binder resin.
Embodiment 12～16; Operating procedure according to embodiment 10; Change the consumption of raw material in the building-up process, it is as shown in table 2 that synthetic cashew nut oil modified Resorcinol class binder resin (R-St-F-CNSL resin), the consumption of raw material and synthetic obtain the performance perameter of R-St-F-CNSL resin.
Synthesizing of table 2R-St-F-CNSL resin
The R-F-CNSL resin that embodiment 1～9 obtains contains following two kinds of structural formulas, and wherein n is 1～100 integer:
The R-F-CNSL resin that embodiment 10～16 obtains contains following two kinds of structural formulas, and wherein n is 1～100 integer:
Claims (9)
1. cashew nut oil modified Resorcinol class binder resin, it comprises following chemical structure:
Wherein R1, R2 can be identical, can be different, can be that H or carbonatoms are a kind of in 1～12 the alkyl, R3 can be that H, carbonatoms are 1～12 alkyl, contain a kind of in the substituent aryl in C1～6, n is 1～100 integer.
2. the preparation method of a cashew nut oil modified Resorcinol class binder resin is characterized in that comprising following steps:
With Resorcinol 120 ℃～130 ℃ fusions; Under an acidic catalyst effect, add aldehyde backflow 15～30min, prepare Resorcinol-aldehyde oligopolymer, add cashew nut shell oil then; Be warming up to 150～180 ℃ of reactions after 1～2 hour; In-0.08MPa underpressure distillation to the-0.10MPa vacuum, remove and anhydrate and the free Resorcinol of part, obtain cashew nut oil modified Resorcinol class binder resin with the neutralizing agent neutralization.
3. the preparation method of a cashew nut oil modified Resorcinol class binder resin is characterized in that and can synthesize cashew nut oil modified Resorcinol class binder resin with the alkylation Resorcinol, and its preparation method is following:
Resorcinol 120～130 ℃ of fusions, under an acidic catalyst effect, is dripped alkene at 120～130 ℃; Make alkene and Resorcinol generation alkylation substitution reaction, obtain content and be mainly the mixture that a replacement Resorcinol and two replaces the Resorcinol alkylation liquids, and then drip aldehyde backflow 15～30min; Prepare alkylation Resorcinol-aldehyde oligopolymer; Add cashew nut shell oil at last, be warming up to 150～180 ℃ of reactions after 1～2 hour, in-0.08MPa underpressure distillation to the-0.10MPa vacuum; Remove and anhydrate and the free Resorcinol of part, obtain cashew nut oil modified Resorcinol class binder resin with the neutralizing agent neutralization.
4. according to claim 2 or 3 described preparing methods, it is characterized in that described cashew nut shell oil is the C15 polyphenol that side chain contains unsaturated double-bond, the consumption of cashew nut shell oil is 0.1%～50% of Resorcinol and a cashew nut shell oil gross weight.
5. according to claim 2 or 3 described preparing methods, it is characterized in that described aldehyde can be a kind of or two or more combinations in formaldehyde, acetaldehyde, butyraldehyde, furfural, isobutyric aldehyde, the Paraformaldehyde 96, the mol ratio of aldehyde and Resorcinol is 0.05～0.80: 1.
6. according to claim 2 or 3 described preparing methods; It is characterized in that described acid catalyst can be a kind of or two or more combinations in tosic acid, alkyl benzene sulphonate(ABS), sulfuric acid, hydrochloric acid, oxalic acid, the thionamic acid, the acid catalyst add-on is 0.3%～3% of a Resorcinol weight.
7. preparation method according to claim 3; It is characterized in that the described alkylating alkene of Resorcinol that is used for is unsaturated olefin or unsaturated diolefine; Be mainly vinylbenzene, alpha-methyl styrene, p-methylstyrene, diisobutylene, isooctene, Vinylstyrene, vinyl naphthalene, a di isopropenylbenzene, to a kind of or two or more combinations in the aromatic compound of di isopropenylbenzene, Vinyl toluene, Vinyl toluene, wherein the mol ratio of Resorcinol and alkene is 1: 0.01～1: 1.
8. according to claim 2 or 3 described preparing methods, it is characterized in that described neutralizing agent is a kind of in NaOH, KOH, organic bases DBU, triethylamine, amine acetate, the trolamine, the neutralizing agent consumption is 0～1.0g.
9. a cashew nut oil modified Resorcinol class binder resin is to adopt any described preparation method in the claim 2 or 3 to prepare.
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| CN102912636A (en) * | 2012-11-01 | 2013-02-06 | 台州宏元工艺有限公司 | Polyamide fibre and aramid fibre gum dipping liquid and production process thereof |
| CN102912635A (en) * | 2012-11-01 | 2013-02-06 | 台州宏元工艺有限公司 | Polyester gum dipping solution and production process thereof |
| FR3017070A1 (en) * | 2014-02-06 | 2015-08-07 | Michelin & Cie | STEEL REINFORCING ELEMENT COATED BY AN ADHESIVE COMPOSITION BASED ON AROMATIC ALDEHYDE AND POLYPHENOL |
| FR3017133A1 (en) * | 2014-02-06 | 2015-08-07 | Michelin & Cie | RUBBER COMPOSITE REINFORCED WITH AT LEAST ONE STEEL REINFORCING ELEMENT ADHESIVED BY AN ADHESIVE COMPOSITION BASED ON AROMATIC ALDEHYDE AND POLYPHENOL |
| CN105085849A (en) * | 2015-08-01 | 2015-11-25 | 江苏麒祥高新材料有限公司 | Modified resorcinol formaldehyde resin adhesion promoter and preparation method thereof |
| CN103626943B (en) * | 2013-12-23 | 2015-12-30 | 于文明 | A kind of preparation method of modified by cardanol alkyl resorcinol formaldehyde resin |
| CN105585679A (en) * | 2014-10-22 | 2016-05-18 | 华奇（中国）化工有限公司 | Cashew nut shell oil modified resorcin-aldehyde resin, and preparing method and applications thereof |
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| CN102912636A (en) * | 2012-11-01 | 2013-02-06 | 台州宏元工艺有限公司 | Polyamide fibre and aramid fibre gum dipping liquid and production process thereof |
| CN103626943B (en) * | 2013-12-23 | 2015-12-30 | 于文明 | A kind of preparation method of modified by cardanol alkyl resorcinol formaldehyde resin |
| CN105939846B (en) * | 2014-02-06 | 2018-03-23 | 米其林集团总公司 | By at least one the rubber composite that the steel reinforcing element of viscosity strengthens is assigned by the adhesive composition containing aromatic aldehyde and polyphenol |
| CN105939846A (en) * | 2014-02-06 | 2016-09-14 | 米其林集团总公司 | Rubber composite reinforced by at least one steel reinforcing element rendered adhesive by adhesive composition containing aromatic aldehyde and polyphenol |
| WO2015118042A1 (en) * | 2014-02-06 | 2015-08-13 | Compagnie Generale Des Etablissements Michelin | Rubber composite reinforced by at least one steel reinforcing element rendered adhesive by an adhesive composition containing aromatic aldehyde and polyphenol |
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| FR3017133A1 (en) * | 2014-02-06 | 2015-08-07 | Michelin & Cie | RUBBER COMPOSITE REINFORCED WITH AT LEAST ONE STEEL REINFORCING ELEMENT ADHESIVED BY AN ADHESIVE COMPOSITION BASED ON AROMATIC ALDEHYDE AND POLYPHENOL |
| FR3017070A1 (en) * | 2014-02-06 | 2015-08-07 | Michelin & Cie | STEEL REINFORCING ELEMENT COATED BY AN ADHESIVE COMPOSITION BASED ON AROMATIC ALDEHYDE AND POLYPHENOL |
| JP2017514010A (en) * | 2014-02-06 | 2017-06-01 | コンパニー ゼネラール デ エタブリッスマン ミシュラン | Steel reinforcement elements coated with adhesive compositions containing aromatic aldehydes and polyphenols |
| WO2015118041A1 (en) * | 2014-02-06 | 2015-08-13 | Compagnie Generale Des Etablissements Michelin | Steel reinforcing element coated with an adhesive composition containing aromatic aldehyde and polyphenol |
| CN105585679A (en) * | 2014-10-22 | 2016-05-18 | 华奇（中国）化工有限公司 | Cashew nut shell oil modified resorcin-aldehyde resin, and preparing method and applications thereof |
| CN105622872A (en) * | 2014-12-15 | 2016-06-01 | 彤程化学（中国）有限公司 | Cashew nut shell oil modified novolac resin and preparation method and application of cashew nut shell oil modified novolac resin |
| CN105085849A (en) * | 2015-08-01 | 2015-11-25 | 江苏麒祥高新材料有限公司 | Modified resorcinol formaldehyde resin adhesion promoter and preparation method thereof |
| CN112592448A (en) * | 2020-12-15 | 2021-04-02 | 北京彤程创展科技有限公司 | Mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin, preparation method thereof, rubber composition and rubber product |
| CN112592448B (en) * | 2020-12-15 | 2022-06-24 | 北京彤程创展科技有限公司 | Mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin, preparation method thereof, rubber composition and rubber product |
| CN117402307A (en) * | 2023-12-15 | 2024-01-16 | 山东永创材料科技有限公司 | Biomass oil modified phenolic resin and preparation method thereof |
| CN117402307B (en) * | 2023-12-15 | 2024-02-09 | 山东永创材料科技有限公司 | Biomass oil modified phenolic resin and preparation method thereof |
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