CN113651846A - Method for modifying rubber by cardanol derivative - Google Patents

Method for modifying rubber by cardanol derivative Download PDF

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CN113651846A
CN113651846A CN202111071273.1A CN202111071273A CN113651846A CN 113651846 A CN113651846 A CN 113651846A CN 202111071273 A CN202111071273 A CN 202111071273A CN 113651846 A CN113651846 A CN 113651846A
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cardanol
rubber
phenolic resin
reacting
derivative
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CN113651846B (en
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谭金和
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Qingyuan High Energy Modified Materials Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/14—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by free hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention relates to the field of rubber modification, and particularly relates to a method for modifying rubber by using a cardanol derivative. The invention firstly provides a preparation method of a cardanol diffractant, which comprises the following steps: s1: reacting the epoxy cardanol with trimethoxy chlorosilane to obtain an intermediate 1; s2: and (3) reacting the intermediate 1 with aminoalkyl trialkoxysilane to obtain the cardanol derivative. According to the invention, the phenolic hydroxyl of the epoxidized cardanol and the epoxy group on the alkyl chain are modified by using silane at the same time to obtain the novel rubber modifier. When the modifier is used for modifying phenolic resin-nitrile rubber, the phenolic resin-nitrile rubber has better bonding property to a glass substrate.

Description

Method for modifying rubber by cardanol derivative
Technical Field
The invention relates to the field of rubber modification, and particularly relates to a method for modifying rubber by using a cardanol derivative.
Background
Cardanol is the main component of cashew nut shell oil, and is the byproduct of cashew nut oil, easy to extract, low in cost, and renewable, and the components in cardanol are roughly as follows (R.Auvergne, S.Caillol, G.David, B.J. -P Pascault, Biobased Thermosettingepoxy: Present and Future, Chemical Reviews 2014,114(2),1082 + 1115.).
Figure BDA0003260194770000011
The structure is that a 15-carbon alkyl chain containing 0-3 double bonds is arranged at the meta position of phenol, phenolic hydroxyl and the alkyl chain have great transformation potential, and the phenol structure of the phenol-formaldehyde resin can also be used as a component of a main chain of the phenol-formaldehyde resin.
CN108586686A discloses an epoxy cardanol/aminosiloxane synergistically modified phenolic resin and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing the epoxy cardanol and phenol, and adding the alkaline catalyst, the aminosiloxane and the paraformaldehyde in batches to prepare the epoxy cardanol/aminosiloxane synergistically modified phenolic resin. The excellent performances of the epoxy cardanol and the amino siloxane are combined, so that the molecular weight increase of the resin modified by the cardanol can be reduced, the viscosity of the synthetic resin is increased rapidly, the fluidity is poor, the microstructure of the subsequent phenolic foam is influenced, and the toughness of the phenolic foam is negatively influenced; meanwhile, halogen-free flame retardant elements, namely nitrogen and silicon, are introduced into the foam structure, so that the problem that the flame retardant property of the cardanol-based phenolic foam is reduced due to the introduction of a long carbon chain of cardanol is solved, and the complex process of additionally adding a flame retardant and the risk of separating out the flame retardant are avoided.
CN111154054A discloses a method for modifying phenolic resin with cardanol and rubber, comprising the following steps: (1) taking raw material phenol as a solvent, and enabling double bonds on a cardanol side chain to have an addition reaction with rubber alpha carbon under the action of an initiator to obtain a mixture of phenol and cardanol grafted rubber; (2) adding formaldehyde and an acid catalyst into the mixture to perform polycondensation reaction on the phenol and the cardanol grafted rubber in the mixture and the formaldehyde; (3) dehydrating to 180 ℃ in vacuum under the condition that the vacuum degree is less than 0.09Mpa, stopping reaction, and discharging to obtain the cardanol and rubber modified phenolic resin. The method can obviously improve the wear resistance, flexibility, compatibility and storage stability of the phenolic resin, and the process adopts a solvent-free process, meets the requirement of environmental protection and does not cause pollution to the environment.
CN113087866A discloses a preparation method and application of cashew phenolic resin. The preparation method comprises the following steps: (1) mixing cardanol, aldehyde substances and a catalyst, and carrying out polymerization reaction to obtain a prepolymer; (2) dehydrating the prepolymer obtained in the step (1), adding an amine compound containing methylene, stirring until a solid is formed, heating, and cooling to obtain a cashew phenolic resin; the catalyst is one of hypophosphorous acid, phosphorous acid or composite acid; the composite acid is a combination of phosphoric acid and sulfurous acid, a combination of phosphoric acid and oxalic acid, or a combination of ammonium hypophosphite and sulfuric acid. By controlling the reaction steps and selecting the catalyst, the yellow cashew phenolic resin can be prepared, and has excellent high-temperature resistance, high mechanical strength and good wear resistance.
It can be seen that when cardanol is used to modify phenolic resin, cardanol is generally used as a component of the main chain of phenolic resin, and is mainly used for increasing toughness and wear resistance of phenolic resin or rubber.
Disclosure of Invention
The invention aims to provide a method for modifying rubber by using a cardanol derivative, which can enable the modified rubber resin to have good adhesive property and is particularly suitable for bonding glass substrates.
The purpose of the invention is realized by the following technical scheme.
In one aspect, the invention provides a preparation method of a cardanol derivative, which comprises the following steps:
s1: reacting the epoxy cardanol with trimethoxy chlorosilane to obtain an intermediate 1;
s2: and (3) reacting the intermediate 1 with aminoalkyl trialkoxysilane to obtain the cardanol derivative.
Further, in S1, the epoxy value of the epoxidized cardanol is 8% to 10%.
Further, in S1, the reaction is carried out in an aprotic solvent.
Further, in S1, the aprotic solvent is at least one selected from benzene, toluene, pyridine, THF, diethyl ether, 1, 4-dioxane, dichloromethane, chloroform, DMF, DMSO, or acetonitrile.
Further, in S1, the molar ratio of the epoxidized cardanol to the trimethoxychlorosilane is 1:1-10, alternatively 1:1-8, 1:1-5, 1:1-3, 1:1-1.5, 1:1-1.2, or 1:1. Preferably 1: 1.1-1.5.
Further, in S1, the reaction is carried out under the condition of excess trimethoxy chlorosilane.
Further, in S1, a base is used in the reaction.
Further, in S1, the base is selected from an organic base, optionally at least one of triethylamine, diisopropylethylamine, or pyridine. Triethylamine is preferred.
Further, in S1, the molar ratio of the epoxidized cardanol to the alkali is 1:1-20, alternatively 1:1-15, 1:1-10, 1:1-5, 1:1-3, 1:1-1.5, or 1:1. Preferably 1: 2-3.
Further, in S2, the aminoalkylalkoxysilane is selected from at least one of aminoethyltrimethoxysilane, aminoethyltriethoxysilane, aminopropyltrimethoxysilane or aminopropyltriethoxysilane.
Further, in S2, the molar ratio of the intermediate 1 to the aminoalkyl trialkoxysilane is 1:0.3 to 0.7, preferably 1: 0.5-0.7.
Further, in S2, the reaction is carried out in an aprotic solvent.
Further, in S2, the aprotic solvent is at least one selected from benzene, toluene, pyridine, THF, diethyl ether, 1, 4-dioxane, dichloromethane, chloroform, DMF, DMSO, or acetonitrile.
Further, the reaction solvents described in S2 and S1 are the same.
Further, in S2, the reaction temperature is 50-70 ℃.
In another aspect, the present invention provides a method for modifying rubber using the cardanol derivative, comprising the steps of:
SS 1: heating and reacting the cardanol derivative with phenolic resin to obtain modified phenolic resin;
SS 2: adding nitrile rubber under the condition of heating to obtain the modified rubber.
Furthermore, in SS1, the mass ratio of the cardanol derivative to the phenolic resin is 1: 3-5.
Furthermore, in SS2, the mass ratio of the nitrile rubber to the cardanol derivative is 10-15: 1.
Further, in SS1 and SS2, the heating temperature is 60 to 100 ℃.
Further, the phenolic resin is a linear phenolic resin and is obtained by polymerizing phenol and formaldehyde, and the polymerization degree is preferably 4-12.
Further, the acrylonitrile-butadiene rubber has an acrylonitrile content of 30-40% and a Mooney viscosity of 70-80.
The invention has the advantages that:
1. according to the invention, the phenolic hydroxyl of the epoxidized cardanol and the epoxy group on the alkyl chain are modified by using silane at the same time to obtain the novel rubber modifier.
2. The modified rubber compounded by the modifier, the phenolic resin and the nitrile rubber has better adhesive property and is particularly suitable for being used on glass substrates.
Detailed Description
Unless otherwise stated, the materials used in the invention are obtained by commercial means, wherein the cardanol four-component content is more than or equal to 99 percent, and the compositions are as follows
Figure BDA0003260194770000031
Calculated, the average relative molecular mass of the cardanol with the composition is 300.68g/mol, and the double bond content is 0.634mol/100 g; if all of the double bonds in the final product are fully epoxidized, the theoretical epoxy value is about 9.68%, which is the theoretical maximum epoxy value.
Preparation method of epoxidized cardanol
Dissolving 100g of cardanol in DCM1000mL, adding 200mL of 30% hydrogen peroxide and 100mL of formic acid, reacting for 5h under the condition of DCM reflux, separating an organic phase after the reaction is finished, washing the organic phase for 2 times with water, wherein the dosage is 200mL each time, drying the organic phase, and removing the solvent under reduced pressure to obtain 95g of epoxidized cardanol with the epoxy value of 9.1%.
Wherein the epoxy value of the epoxidized cardanol can be adjusted by changing parameter conditions in the method according to needs.
The method for detecting the epoxy value in the present invention is referred to GB/T1677-2008 "determination of epoxy value of plasticizer", and the epoxy value is defined as "the content of oxygen in an oxirane group per 100g of sample, and is referred to as the epoxy value".
Example 1
Preparation method of cardanol derivative
1mol of epoxidized cardanol and 1.5mol of trimethoxy chlorosilane are dissolved in 2000ml of THF, 2mol of triethylamine is added, and reaction is carried out for 12 hours. The solvent and excess trimethoxychlorosilane were removed under reduced pressure to give a residue containing intermediate 1. DMF3000mL was added and stirred well, followed by the addition of 0.3mol of aminoethyl trimethoxysilane, heating to 70 ℃ and reaction for 4 h. After completion of the reaction, DMF was removed under reduced pressure to obtain a residue containing the cardanol derivative, and the residue was suspended in 1000mL of ethyl acetate, stirred uniformly, and then filtered. And removing ethyl acetate from the filtrate under reduced pressure to obtain the cardanol derivative.
Preparation of modified rubber using the cardanol derivative
Taking 100g of the cardanol derivative, adding 500g of linear phenolic resin (with the polymerization degree of 6), heating to 80 ℃, reacting for 3h, adding 1200g of nitrile rubber (JSR N232SH, ACN ═ 35, Mooney viscosity of 77), continuously keeping 80 ℃, reacting for 2h, and cooling to 20-30 ℃ to obtain the modified rubber.
Example 2
Preparation method of cardanol derivative
1mol of epoxidized cardanol and 1.1mol of trimethoxy chlorosilane are dissolved in 2000mL of chloroform, 2mol of triethylamine is added, and the reaction is carried out for 8 hours. The solvent and excess trimethoxychlorosilane were removed under reduced pressure to give a residue containing intermediate 1. Adding 3000mL of toluene, stirring uniformly, then adding 0.7mol of aminopropyl trimethoxy silane, heating to 60 ℃, and reacting for 6 h. After completion of the reaction, toluene was removed under reduced pressure to obtain a residue containing the cardanol derivative, and the residue was suspended in 1000mL of ethyl acetate, stirred uniformly, and then filtered. And removing ethyl acetate from the filtrate under reduced pressure to obtain the cardanol derivative.
Preparation of modified rubber using the cardanol derivative
Taking 100g of the cardanol derivative, adding 300g of linear phenolic resin (with the polymerization degree of 10), heating to 80 ℃, reacting for 3h, adding 1200g of nitrile rubber (JSR N236H, ACN ═ 32, Mooney viscosity of 72), continuously keeping 80 ℃, reacting for 2h, and cooling to 20-30 ℃ to obtain the modified rubber.
Example 3
1mol of epoxidized cardanol and 2mol of trimethoxy chlorosilane are dissolved in 3000mL of pyridine and reacted for 8 hours. The solvent and excess trimethoxychlorosilane were removed under reduced pressure to give a residue containing intermediate 1. THF (3000 mL) is added and stirred uniformly, then aminopropyltrimethoxysilane (0.5 mol) is added, the temperature is raised to 70 ℃, and the reaction is carried out for 6 h. After completion of the reaction, THF was removed under reduced pressure to obtain a residue containing the cardanol derivative, and the residue was suspended in 1000mL of ethyl acetate, stirred well, and then filtered. And removing ethyl acetate from the filtrate under reduced pressure to obtain the cardanol derivative.
Preparation of modified rubber using the cardanol derivative
Taking 100g of the cardanol derivative, adding 500g of linear phenolic resin (with the polymerization degree of 10), heating to 80 ℃, reacting for 3h, adding 1200g of nitrile rubber (JSR N224SH, ACN ═ 37, Mooney viscosity of 70), continuously keeping 80 ℃, reacting for 2h, and cooling to 20-30 ℃ to obtain the modified rubber.
Comparative example 1
The difference from example 1 is that in preparing the modified rubber, epoxidized cardanol is used instead of the cardanol derivative.
Comparative example 2
The difference from example 1 is that aminopropyltrimethoxysilane was used in an amount of 1 mol.
Comparative example 3
The difference from example 1 is that no trimethoxychlorosilicon was used for the modification.
Examples of effects
The adhesive properties of the products were evaluated using the shear strength test. Specifically referring to determination of tensile shear strength (rigid material to rigid material) of GB/T7124-.
Table 1 tensile shear strength data
Figure BDA0003260194770000051
It can be seen that when the cardanol derivative is used for modifying phenolic resin-nitrile rubber, the rubber obtained through modification has good bonding performance on a glass substrate. From the data of comparative example 2, it can be seen that when the amount of aminoalkylalkoxysilane used in the preparation of the derivative is too large, the cardanol derivative may lose a certain crosslinking property, and the binding ability of the final modified rubber may be reduced; the data of comparative example 3 shows that the derivatization of the cardanol hydroxyl group in the application also has a large influence on the final gluing effect.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. A preparation method of cardanol derivatives comprises the following steps:
s1: reacting the epoxy cardanol with trimethoxy chlorosilane to obtain an intermediate 1;
s2: and (3) reacting the intermediate 1 with aminoalkyl trialkoxysilane to obtain the cardanol derivative.
2. The method according to claim 1, wherein in S1, the epoxidizing value of the epoxidizing cardanol is 8% to 10%.
3. The method according to claim 1, wherein the reaction is carried out in an aprotic solvent in S1.
4. The method according to claim 3, wherein the aprotic solvent in S1 is at least one selected from the group consisting of benzene, toluene, pyridine, THF, diethyl ether, 1, 4-dioxane, dichloromethane, chloroform, DMF, DMSO and acetonitrile.
5. The preparation method according to claim 1, wherein in S1, the molar ratio of the epoxidized cardanol to the trimethoxychlorosilane is 1: 1-10.
6. The method according to claim 1, wherein a base is used in the reaction in S1.
7. The method according to claim 1, wherein in S2, the aminoalkylalkoxysilane is at least one selected from the group consisting of aminoethyltrimethoxysilane, aminoethyltriethoxysilane, aminopropyltrimethoxysilane and aminopropyltriethoxysilane.
8. The method according to claim 1, wherein the molar ratio of intermediate 1 to aminoalkyltrialkoxysilane in S2 is 1: 0.3-0.7.
9. The method according to claim 1, wherein, in S2, the reaction is carried out in an aprotic solvent;
preferably, the aprotic solvent is selected from at least one of benzene, toluene, pyridine, THF, diethyl ether, 1, 4-dioxane, dichloromethane, chloroform, DMF, DMSO, or acetonitrile.
10. A method for modifying rubber with a cardanol derivative obtained by the production method according to any one of claims 1 to 9, comprising the steps of:
SS 1: heating and reacting the cardanol derivative with phenolic resin to obtain modified phenolic resin;
SS 2: adding nitrile rubber under the condition of heating to obtain the modified rubber.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114605259A (en) * 2022-02-24 2022-06-10 江苏麒祥高新材料有限公司 Modified cashew nut oil, rubber plasticizer, and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103554442A (en) * 2013-11-20 2014-02-05 哈尔滨师范大学 Cardanol derivative curing agent and preparation method thereof
CN103554063A (en) * 2013-11-06 2014-02-05 河南省化工研究所有限责任公司 Preparation method of cardanol glycidyl ether with high epoxy value
WO2021037799A1 (en) * 2019-08-28 2021-03-04 Basf Coatings Gmbh A cardanol-derivatives modified polymer and a coating composition comprising the same
CN112794828A (en) * 2021-01-13 2021-05-14 广东宏力达合成材料科技有限公司 Epoxidized dicamba carbonate type plasticizer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103554063A (en) * 2013-11-06 2014-02-05 河南省化工研究所有限责任公司 Preparation method of cardanol glycidyl ether with high epoxy value
CN103554442A (en) * 2013-11-20 2014-02-05 哈尔滨师范大学 Cardanol derivative curing agent and preparation method thereof
WO2021037799A1 (en) * 2019-08-28 2021-03-04 Basf Coatings Gmbh A cardanol-derivatives modified polymer and a coating composition comprising the same
CN112794828A (en) * 2021-01-13 2021-05-14 广东宏力达合成材料科技有限公司 Epoxidized dicamba carbonate type plasticizer

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114605259A (en) * 2022-02-24 2022-06-10 江苏麒祥高新材料有限公司 Modified cashew nut oil, rubber plasticizer, and preparation method and application thereof

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