CN111116627A - Multifunctional silane coupling agent, preparation thereof and application thereof in flame-retardant natural rubber - Google Patents
Multifunctional silane coupling agent, preparation thereof and application thereof in flame-retardant natural rubber Download PDFInfo
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- CN111116627A CN111116627A CN201911296234.4A CN201911296234A CN111116627A CN 111116627 A CN111116627 A CN 111116627A CN 201911296234 A CN201911296234 A CN 201911296234A CN 111116627 A CN111116627 A CN 111116627A
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- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 75
- 239000003063 flame retardant Substances 0.000 title claims abstract description 30
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 244000043261 Hevea brasiliensis Species 0.000 title claims abstract description 21
- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 21
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 21
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 18
- 239000012796 inorganic flame retardant Substances 0.000 claims abstract description 15
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical group [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 34
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- -1 acryloyloxy hydrocarbon Chemical class 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000003444 phase transfer catalyst Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 238000011033 desalting Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical group [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 4
- 229910001414 potassium ion Chemical group 0.000 claims description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 238000005576 amination reaction Methods 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- 238000010306 acid treatment Methods 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims 4
- 239000004215 Carbon black (E152) Substances 0.000 claims 3
- 229930195733 hydrocarbon Natural products 0.000 claims 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 34
- 238000005859 coupling reaction Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 10
- 230000008878 coupling Effects 0.000 abstract description 8
- 238000010168 coupling process Methods 0.000 abstract description 8
- 230000020169 heat generation Effects 0.000 abstract description 5
- 238000007670 refining Methods 0.000 abstract description 5
- 238000007906 compression Methods 0.000 abstract description 4
- 230000006835 compression Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 55
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 51
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 34
- 238000003756 stirring Methods 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 229910052757 nitrogen Inorganic materials 0.000 description 27
- 239000002904 solvent Substances 0.000 description 27
- 238000001035 drying Methods 0.000 description 26
- 238000001914 filtration Methods 0.000 description 26
- 239000000706 filtrate Substances 0.000 description 23
- 238000001816 cooling Methods 0.000 description 18
- 239000012044 organic layer Substances 0.000 description 18
- 239000000376 reactant Substances 0.000 description 18
- 239000003960 organic solvent Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 238000005303 weighing Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000005457 ice water Substances 0.000 description 9
- 238000002390 rotary evaporation Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- DZGWFCGJZKJUFP-UHFFFAOYSA-N tyramine Chemical compound NCCC1=CC=C(O)C=C1 DZGWFCGJZKJUFP-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 5
- AOGDNNLIBAUIIX-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-1-ylbenzene-1,4-diamine Chemical compound C1=CC=C2C(NC=3C=CC(NC=4C5=CC=CC=C5C=CC=4)=CC=3)=CC=CC2=C1 AOGDNNLIBAUIIX-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 2
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 2
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MFIUDWFSVDFDDY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 MFIUDWFSVDFDDY-UHFFFAOYSA-M 0.000 description 2
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- QRPRIOOKPZSVFN-UHFFFAOYSA-M methyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 QRPRIOOKPZSVFN-UHFFFAOYSA-M 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 2
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 2
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000003190 viscoelastic substance Substances 0.000 description 1
Classifications
-
- 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
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5477—Silicon-containing compounds containing nitrogen containing nitrogen in a heterocyclic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a multifunctional silane coupling agent, a preparation method thereof and application thereof in flame-retardant natural rubber. The multifunctional silane coupling agent contains cyclic silicon nitrogen group and (methyl) acryloyloxy hydrocarbyl functional group, can simultaneously modify inorganic flame retardant hydrated metal oxide and rubber, does not need high-temperature heat refining on rubber materials, has high coupling efficiency, fully realizes the effect of inorganic flame retardant rubber, effectively improves the tensile strength and stress at definite elongation of the rubber materials while keeping the flame retardant performance, obviously reduces the compression permanent deformation, and obviously improves the heat generation performance and the creep performance.
Description
Technical Field
The invention belongs to the technical field of synthesis of silane coupling agents, and particularly relates to a multifunctional silane coupling agent and a preparation method and application thereof.
Background
In recent years, fire disasters occur in various countries due to ignition of materials, so that the flame retardance of the materials is an important problem which is generally concerned. In order to enable rubber and rubber products to reach a more ideal flame retardant grade, a flame retardant is mainly added into rubber by a mechanical mixing method in the rubber industry at present, and multiple flame retardants are generally adopted for compounding and are added in a larger amount. Flame retardants can be divided into organic flame retardants and inorganic flame retardants, wherein the inorganic flame retardants mainly comprise hydrated metal oxides such as aluminum hydroxide, borides such as hydrated zinc borate, hydrated silicates such as montmorillonite, and the like. Due to poor compatibility with rubber, the addition of flame retardants, especially a large amount of inorganic flame retardants, often results in reduced mechanical properties, increased heat generation and creep of rubber compounds, and the like, which seriously affects the functions and uses of rubber products.
Silane coupling agent is used as a typical inorganic particle surface treatment agent, organic functional groups capable of being combined with rubber and hydrolyzable functional groups capable of being combined with inorganic materials are arranged in molecules, and mutual inert rubber and inorganic materials form 'bridge bonds' through chemical reaction or physical action, so that the silane coupling agent plays a role in enhancing the bonding force between the rubber and the inorganic material interface and improving the performance of composite materials, and is widely applied to surface treatment of flame retardants. However, when the conventional silane coupling agent is used for processing a sizing material containing a large amount of inorganic flame retardant, high-temperature heat refining is often needed, and the coupling efficiency is still to be further improved. Therefore, the design and synthesis of the multifunctional silane coupling agent which can modify inorganic flame retardant and rubber simultaneously without heat refining and has high coupling efficiency have very important significance.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings in the background technology and providing a multifunctional silane coupling agent, a preparation method and application thereof, which can be used for modifying inorganic flame retardant and rubber at the same time without heat refining and has high coupling efficiency.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a multifunctional silane coupling agent contains a cyclic silazane group and a (methyl) acryloyloxy hydrocarbyl functional group in a molecular structure.
In the above silane coupling agent, preferably, the cyclic silicon nitrogen functional group includes one or more of a cyclic dialkoxysilane group, a cyclic alkylalkoxysilazane group, and a cyclic dialkoxysilane group. The (meth) acryloyloxyhydrocarbyl functional group comprises one or more of acryloyloxyhydrocarbyl and methacryloyloxycarbyl.
Preferably, the multifunctional silane coupling agent has a molecular structural formula:
wherein x is 0, 1 or 2, R1、R2Are identical or different straight-chain or branched alkyl radicals of 1 to 10 carbon atoms, preferably C1 to C3, R3Is a linear or branched alkyl group of 1 to 15 carbon atoms (preferably C1 to C3), R4Is a linear or branched alkyl group of 1 to 18 carbon atoms, preferably C1 to C3, R5Is methyl or hydrogen.
As a general inventive concept, the present invention also provides a method for preparing a multifunctional silane coupling agent, wherein the molecular structural formula is (R)1O)3-xSiR2 xR3The compound and the molecular structural formula of X are NH2R4The compound of X is subjected to amination reaction to prepare (R)1O)3-xSiR2 xR3NHR4X, will (R)1O)3-xSiR2 xR3NHR4X and the molecular structural formula is CH2＝CR5COOM compound is subjected to desalting condensation reaction under the action of a phase transfer catalyst to prepare (R)1O)3-xSiR2 xR3NHR4OOCR5C＝CH2Will (R)1O)3- xSiR2 xR3NHR4OOCR5C＝CH2Dealcoholizing under the action of ammonium salt to obtain the multifunctional silane coupling agent: (R)1O)2- xSiR2 xR3NR4OOCR5C＝CH2(ii) a Wherein X is 0, 1 or 2, X is Cl, Br or I, M is sodium ion or potassium ion, R is1、R2Are identical or different straight-chain or branched alkyl radicals of 1 to 10 carbon atoms, preferably C1 to C3, R3Is a linear or branched alkyl group of 1 to 15 carbon atoms (preferably C1 to C3), R4Is a linear or branched alkyl group of 1 to 18 carbon atoms, preferably C1 to C3, R5Is methyl or hydrogen.
The preparation method preferably comprises the following steps:
(1) the molecular structural formula is [ HCl ]]·NH2R4The compound of X is subjected to desalting and acid treatment in an alkali solution to obtain a compound with a molecular structural formula of NH2R4A compound of X;
(2) reacting NH2R4X and the molecular structural formula is (R)1O)3-xSiR2 xR3Carrying out amination reaction on the compound of X to obtain a compound with a molecular structural formula of (R)1O)3-xSiR2 xR3NHR4A compound of X; the NH2R4X and (R)1O)3-xSiR2 xR3The molar ratio of X is (1-5): 1;
(3) will (R)1O)3-xSiR2 xR3NHR4X and the molecular structural formula is CH2＝CR5The compound of COOM is subjected to desalting condensation reaction under the action of a phase transfer catalyst,to obtain a molecular structural formula of (R)1O)3-xSiR2 xR3NHR4OOCR5C＝CH2A compound of (1); said (R)1O)3-xSiR2 xR3NHR4X and CH2＝CR5The amounts of COOM and phase transfer catalyst are 1: (1-3) (molar ratio), 1: (0.1-5%) (mass ratio);
(4) will (R)1O)3-xSiR2 xR3NHR4OOCR5C＝CH2Dealcoholizing under the action of ammonium salt to obtain the multifunctional silane coupling agent: (R)1O)2-xSiR2 xR3NR4OOCR5C＝CH2(ii) a Said (R)1O)3-xSiR2 xR3NHR4OOCR5C＝CH2And ammonium salt in a molar ratio of 1: (1/20-1).
In the preparation method, preferably, the specific operation process of the step (1) is as follows: in an alkali solution (preferably K) with the concentration of 2-40 wt%2CO3KOH, NaOH or NH4OH) to [ HCl ]]·NH2R4X, stirring for 0.1-3 h (preferably 0.3-2.5 h) in ice-water bath, adding an organic solvent for extraction for 2-5 times (preferably 3-4 times), and combining organic layers; then washing the organic layer with saturated sodium chloride aqueous solution for 1-5 times (preferably 2-4 times), adding anhydrous magnesium sulfate, stirring, drying, filtering, removing the organic solvent by rotary evaporation of the filtrate, and drying in vacuum at 10-40 ℃ to constant weight to obtain the compound with the molecular structural formula of NH2R4A compound of X; the organic solvent is diethyl ether, ethyl acetate, dichloromethane or trichloromethane.
In the preparation method, preferably, the specific operation process of the step (2) is as follows: under the protection of nitrogen, mixing the components in a molar ratio of 1: (1-5) of (R)1O)3-xSiR2 xR3X and NH2R4Adding X into an organic solvent, stirring, heating to 60-150 ℃ (preferably 80-120 ℃) for reaction for 12-48 h (preferably 12-36 h), standing and cooling after the reaction is finished, filtering, and enabling the filtrate to be at 50-90 DEG C(preferably 55-80 ℃) and removing residual reactants and solvent by reduced pressure distillation, and drying the mixture in vacuum to constant weight at 10-40 ℃ (preferably 20-35 ℃) to obtain the compound with the molecular structural formula of (R)1O)3-xSiR2 xR3NHR4A compound of X; the organic solvent is dimethyl sulfoxide, dimethylformamide, tetrahydrofuran or toluene.
In the preparation method, preferably, the specific operation process of the step (3) is as follows: under the protection of nitrogen, mixing the components in a molar ratio of 1: (1-3) (preferably 1 (1-2)) (R)1O)3-xSiR2 xR3NHR4X and CH2＝CR5COOM (M is sodium ion or potassium ion, preferably potassium ion) is added into the organic solvent, and phase transfer catalyst and polymerization inhibitor (phase transfer catalyst, polymerization inhibitor and (R) are added under stirring1O)3-xSiR2 xR3NHR4The mass ratio of X is respectively (0.1-5%, preferably 0.8-2%): (0.001% to 5%, preferably 0.1% to 0.5%): 1) heating to 80-130 ℃ (preferably 100-125 ℃) for reaction for 0.5-4 h (preferably 1-3 h), standing and cooling after the reaction is finished, filtering, distilling the filtrate under reduced pressure at 50-90 ℃ (preferably 55-80 ℃) to remove residual reactants and solvent, and drying under vacuum at 10-40 ℃ (preferably 20-35 ℃) to constant weight to obtain the compound with the molecular structural formula of (R)1O)3- xSiR2 xR3NHR4OOCR5C＝CH2A compound of (1); the phase transfer catalyst is a quaternary ammonium salt such as tetrabutylammonium iodide, tetrabutylammonium bromide, or a quaternary phosphonium salt such as tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetraphenylphosphonium chloride, methyltriphenylphosphonium chloride, butyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, etc.; the polymerization inhibitor is one or more of phenolic compounds such as 2, 6-di-tert-butyl-4-methylphenol, aromatic secondary amino compounds such as N, N' -dinaphthyl p-phenylenediamine and aminoalkylene phenolic compounds such as 4- (2-aminoethyl) phenol; the organic solvent is dimethylformamide or toluene.
In the preparation method, preferably, the specific operation process of the step (4) is as follows: under the protection of nitrogen, the nitrogen gas is used for protecting the reaction vessel,mixing a mixture of 1: (1/20-1) (preferably 1 (1/15-1/5)) (R)1O)3-xSiR2 xR3NHR4OOCR5C＝CH2And inorganic ammonium salts (e.g., (NH)4)2SO4) Adding the mixture into an organic solvent, stirring, heating to 80-130 ℃ (preferably 100-125 ℃), carrying out reflux reaction for 1-24 h (preferably 1.5-12 h), and after the reaction is finished, carrying out reduced pressure distillation at 55-90 ℃ (preferably 60-85 ℃) to remove the solvent and byproduct micromolecule organic alcohol to obtain the multifunctional silane coupling agent: (R)1O)2-xSiR2 xR3NR4OOCR5C＝CH2(ii) a The organic solvent is dimethyl sulfoxide, dimethylformamide or toluene.
As a general inventive concept, the present invention also provides an application of the multifunctional silane coupling agent or the multifunctional silane coupling agent obtained by the preparation method in a flame-retardant natural rubber composite material, wherein the flame-retardant natural rubber composite material is natural rubber added with an inorganic flame retardant which is a hydrated metal oxide.
In the above application, preferably, the hydrated metal oxide is aluminum hydroxide or magnesium hydroxide, etc.
The cyclic silicon nitrogen functional groups in the molecule of the multifunctional silane coupling agent, such as cyclic dialkoxyl silicon nitrogen groups, cyclic alkyl alkoxy silicon nitrogen groups, cyclic dialkyl silicon nitrogen groups and the like, do not need water as a catalyst, can quickly perform ring-opening reaction with the adjacent hydroxyl groups forming hydrogen bonds on the surface of the inorganic flame retardant hydrated metal oxide at room temperature, and can quickly perform ring-opening reaction (namely modify the flame retardant) with the isolated hydroxyl groups not forming hydrogen bonds on the surface of the hydrated metal oxide, so the coupling efficiency is high, and no byproduct, namely small molecular organic alcohol and the like are generated; the (meth) acryloyloxyhydrocarbyl functional group such as acryloyloxyhydrocarbyl and methacryloyloxycarbyl in the molecule of the coupling agent can form a free radical at high temperature to participate in the vulcanization reaction of the rubber (i.e. to modify the rubber). Therefore, the multifunctional silane coupling agent molecule contains the cyclic silazane group and the (methyl) acryloyloxy hydrocarbyl functional group at the same time, can efficiently perform coupling reaction with the hydrated metal oxide at room temperature to realize the modification of the hydrated metal oxide, can also perform chemical reaction with rubber during vulcanization to realize the modification of the hydrated metal oxide, bridges a bridge bond between the hydrated metal oxide and the rubber, enhances the bonding force between the hydrated metal oxide and the rubber, improves the dispersibility of the hydrated metal oxide in a rubber matrix, and fully realizes the effect of the inorganic flame retardant on flame retardant rubber.
If the 2 kinds of functional groups are not contained simultaneously, for example, the functional groups do not contain cyclic silicon nitrogen groups, the coupling reaction with isolated hydroxyl groups which do not form hydrogen bonds on the surface of the hydrated metal oxide cannot be carried out, the coupling efficiency is not high, and the sizing material needs to be heated at high temperature to ensure the modification of the hydrated metal oxide; if the (meth) acryloyloxyhydrocarbyl functional group is not contained, the rubber cannot be modified. In the rubber compound containing a large amount of hydrated metal oxide, in the above 2 cases, a "bridge bond" cannot be efficiently and conveniently formed between the hydrated metal oxide and the rubber, and the flame retardant effect cannot be sufficiently achieved.
Compared with the prior art, the invention has the beneficial effects that:
(1) the multifunctional silane coupling agent contains cyclic silicon nitrogen group and (methyl) acryloyloxy hydrocarbyl functional group, can simultaneously modify inorganic flame retardant hydrated metal oxide and rubber, does not need high-temperature heat refining on rubber materials, has high coupling efficiency, fully realizes the effect of inorganic flame retardant rubber, effectively improves the tensile strength and stress at definite elongation of the rubber materials while keeping the flame retardant performance, obviously reduces the compression permanent deformation, and obviously improves the heat generation performance and the creep performance.
(2) The preparation method has high universality, is simple and easy to operate, and can share organic synthesis instrument equipment; the rubber material directly adopts the conventional mixing process, realizes the modification of the inorganic flame retardant hydrated metal oxide and the rubber in the mixing and vulcanizing process, has simple process, small environmental pollution and high equipment universality compared with high-temperature hot mixing, and has good market application value in the rubber industry field.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the preparation method of the multifunctional silane coupling agent comprises the following steps:
(1)[HCl]·NH2(CH2)3cl for hydrochloric acid: preparing 10% KOH solution, adding [ HCl ]]·NH2(CH2)3Cl, stirring for 1 hour in ice-water bath; adding ethyl acetate, extracting for 3 times, and mixing organic layers; washing the organic layer with saturated sodium chloride water solution for 4 times, adding anhydrous magnesium sulfate, stirring, drying for one day and night, filtering, removing organic solvent by rotary evaporation, and vacuum drying at 30 deg.C to constant weight to obtain NH2(CH2)3Cl。
(2) 24g of gamma-chloropropyltriethoxysilane ((C) was weighed2H5O)3Si(CH2)3Cl)、10gNH2(CH2)3Adding Cl and 95g of dimethylformamide into a three-neck round-bottom flask under the protection of nitrogen, stirring, slowly heating, and reacting for 24 hours at 110 ℃; after the reaction is finished, standing and cooling, filtering, distilling the filtrate at 70 ℃ under reduced pressure to remove residual reactants and solvent, and drying at 30 ℃ in vacuum to constant weight to obtain the multifunctional silane coupling agent with the molecular formula of (C)2H5O)3Si(CH2)3NH(CH2)3Cl, yield about 99%.
(3) Weighing 30g (C)2H5O)3Si(CH2)3NH(CH2)3Cl、13gCH2＝C(CH3) COOK and 75g of dimethylformamide are added into a three-neck round-bottom flask under the protection of nitrogen, 0.3g of tetrabutyl phosphonium chloride and 0.3g of N, N' -dinaphthyl p-phenylenediamine are added under stirring, and the temperature is raised to 110 ℃ for reaction for 2.5 hours; after the reaction is finished, standing and cooling, filtering, distilling the filtrate at 70 ℃ under reduced pressure to remove residual reactants and solvent, and drying at 30 ℃ in vacuum to constant weight to obtain the multifunctional silane coupling agent with the molecular formula of (C)2H5O)3Si(CH2)3NH(CH2)3OOC(CH3)C＝CH2The yield was about 98%.
(4) Weighing 35g (C)2H5O)3Si(CH2)3NH(CH2)3OOC(CH3)C＝CH2、0.9g(NH4)2SO4And 85g of dimethylformamide are added into a three-neck round-bottom flask under the protection of nitrogen, stirred, slowly heated and refluxed for 6 hours at the temperature of 110 ℃. After the reaction is finished, the solvent and the byproduct micromolecular organic alcohol are removed by reduced pressure distillation at 70 ℃ to obtain the multifunctional silane coupling agent with the molecular formula of (C)2H5O)2Si(CH2)3N(CH2)3OOC(CH3)C＝CH2(ii) a The product name is C1 for short, and the yield is about 97 percent.
Example 2:
the preparation method of the multifunctional silane coupling agent comprises the following steps:
(1)[HCl]·NH2(CH2)3cl for hydrochloric acid: preparing 15% NaOH aqueous solution, adding [ HCl ]]·NH2(CH2)3Cl, stirring for 2 hours in ice-water bath; adding dichloromethane for extraction for 4 times, and combining organic layers; washing the organic layer with saturated sodium chloride water solution for 4 times, adding anhydrous magnesium sulfate, stirring, drying for one day and night, filtering, removing organic solvent by rotary evaporation, and vacuum drying at 25 deg.C to constant weight to obtain NH2(CH2)3Cl。
(2) 20g of gamma-chloropropyltrimethoxysilane ((CH)3O)3Si(CH2)3Cl)，15gNH2(CH2)3Adding Cl and 90g of toluene into a three-neck round-bottom flask under the protection of nitrogen, stirring, slowly heating, and reacting for 24 hours at 100 ℃; after the reaction is finished, standing and cooling, filtering, distilling the filtrate at 60 ℃ under reduced pressure to remove residual reactants and solvent, and drying at 25 ℃ in vacuum to constant weight to obtain the multifunctional silane coupling agent with the molecular formula of (CH)3O)3Si(CH2)3NH(CH2)3Cl, yield about 99%.
(3) Weighing 26g (CH)3O)3Si(CH2)3NH(CH2)3Cl、14gCH2＝C(CH3) COOK and 65g of toluene are added into a three-neck round-bottom flask under the protection of nitrogen, 0.3g of tetrabutyl phosphonium bromide and 0.4g of 2, 6-di-tert-butyl-4-methylphenol are added under stirring, and the temperature is raised to 110 ℃ for reaction for 2.5 hours; after the reaction is finished, standing and cooling, filtering, distilling the filtrate at 60 ℃ under reduced pressure to remove residual reactants and solvent, and drying at 25 ℃ in vacuum to constant weight to obtain the multifunctional silane coupling agent with the molecular formula of (CH)3O)3Si(CH2)3NH(CH2)3OOC(CH3)C＝CH2The yield was about 98%.
(4) Weighing 30g (CH)3O)3Si(CH2)3NH(CH2)3OOC(CH3)C＝CH2、1.3g(NH4)2SO4And 75g of toluene are added into a three-neck round-bottom flask under the protection of nitrogen, stirred, slowly heated and refluxed for 6 hours at the temperature of 110 ℃. After the reaction is finished, the solvent and the byproduct micromolecular organic alcohol are removed by reduced pressure distillation at 60 ℃ to obtain the multifunctional silane coupling agent with the molecular formula of (CH)3O)2Si(CH2)3N(CH2)3OOC(CH3)C＝CH2(ii) a The product name is C2 for short, and the yield is about 97 percent.
Example 3:
the preparation method of the multifunctional silane coupling agent comprises the following steps:
(1)[HCl]·NH2(CH2)3cl for hydrochloric acid: preparing ammonia with the concentration of 20%Aqueous solution, adding [ HCl ]]·NH2(CH2)3Cl, stirring for 2.5 hours in ice-water bath; adding ether for extraction for 4 times, and mixing organic layers; washing the organic layer with saturated sodium chloride water solution for 3 times, adding anhydrous magnesium sulfate, stirring and drying for one day and night, filtering, removing organic solvent from the filtrate by rotary evaporation, and vacuum drying at 20 deg.C to constant weight to obtain NH2(CH2)3Cl。
(2) 18g of gamma-chloropropylmethyldimethoxysilane ((CH)3O)2CH3Si(CH2)3Cl)、20gNH2(CH2)3Cl and 110g of dimethyl sulfoxide (DCSO) are added into a three-neck round-bottom flask under the protection of nitrogen, stirred and slowly heated to react for 12 hours at 120 ℃. After the reaction is finished, standing and cooling, filtering, distilling the filtrate at 80 ℃ under reduced pressure to remove residual reactants and solvent, and drying under vacuum at 35 ℃ to constant weight to obtain the multifunctional silane coupling agent with the molecular formula of (CH)3O)2CH3Si(CH2)3NH(CH2)3Cl, yield about 99%.
(3) Weighing 24g (CH)3O)2CH3Si(CH2)3NH(CH2)3Cl、12gCH2Adding CHCOOK and 50g of dimethylformamide into a three-neck round-bottom flask under the protection of nitrogen, adding 0.4g of methyl triphenyl phosphonium chloride and 0.5g of 4- (2-aminoethyl) phenol under stirring, and heating to 115 ℃ for reacting for 2 hours; after the reaction is finished, standing and cooling, filtering, distilling the filtrate at 70 ℃ under reduced pressure to remove residual reactants and solvent, and drying at 30 ℃ in vacuum to constant weight to obtain the multifunctional silane coupling agent with the molecular formula of (CH)3O)2CH3Si(CH2)3NH(CH2)3OOCCH＝CH2The yield was about 98%.
(4) 27g (CH) are weighed3O)2CH3Si(CH2)3NH(CH2)3OOCCH＝CH2、2g(NH4)2SO4And 68g of dimethyl sulfoxide are added into a three-neck round-bottom flask under the protection of nitrogen, stirred, slowly heated and refluxed for reaction for 3 hours at 125 ℃. The reaction is finishedThen, the solvent and the byproduct micromolecular organic alcohol are removed by reduced pressure distillation at the temperature of 80 ℃, and the multifunctional silane coupling agent with the molecular formula of (CH) is obtained3O)CH3Si(CH2)3N(CH2)3OOCCH＝CH2(ii) a The product name is C3 for short, and the yield is about 97 percent.
Example 4:
the preparation method of the multifunctional silane coupling agent comprises the following steps:
(1)[HCl]·NH2(CH2)3cl for hydrochloric acid: k with the preparation concentration of 30%2CO3Solution, adding [ HCl ]]·NH2(CH2)3Cl, stirring for 2 hours in ice-water bath; adding chloroform for extraction for 3 times, and combining organic layers; washing the organic layer with saturated sodium chloride water solution for 3 times, adding anhydrous magnesium sulfate, stirring and drying for one day and night, filtering, removing organic solvent from the filtrate by rotary evaporation, and vacuum drying at 30 deg.C to constant weight to obtain NH2(CH2)3Cl。
(2) 18g of gamma-chloropropylethoxydimethylsilane ((C) were weighed2H5O)(CH3)2Si(CH2)3Cl)、25gNH2(CH2)3Cl and 95g of dimethylformamide are added into a three-neck round-bottom flask under the protection of nitrogen, stirred and slowly heated to react for 24 hours at 110 ℃. After the reaction is finished, standing and cooling, filtering, distilling the filtrate at 70 ℃ under reduced pressure to remove residual reactants and solvent, and drying at 30 ℃ in vacuum to constant weight to obtain the multifunctional silane coupling agent with the molecular formula of (C)2H5O)(CH3)2Si(CH2)3NH(CH2)3Cl, yield about 99%.
(3) Weighing 24g (C)2H5O)(CH3)2Si(CH2)3NH(CH2)3Cl、13gCH2Adding CHCOOK and 45g of dimethylformamide into a three-neck round-bottom flask under the protection of nitrogen, adding 0.5g of butyltriphenylphosphonium chloride and 0.7g of N, N' -dinaphthyl p-phenylenediamine under stirring, and heating to 120 ℃ to react for 1.5 h; after the reaction is finished, standing, cooling, filtering and filteringDistilling the solution at 70 deg.C under reduced pressure to remove residual reactant and solvent, and vacuum drying at 30 deg.C to constant weight to obtain multifunctional silane coupling agent with molecular formula of (C)2H5O)(CH3)2Si(CH2)3NH(CH2)3OOCCH＝CH2The yield was about 98%.
(4) 27g (C) are weighed2H5O)(CH3)2Si(CH2)3NH(CH2)3OOCCH＝CH2、2.6g(NH4)2SO4And 68g of dimethylformamide are added into a three-neck round-bottom flask under the protection of nitrogen, stirred, slowly heated and refluxed for 4 hours at 120 ℃. After the reaction is finished, the solvent and the byproduct micromolecular organic alcohol are removed by reduced pressure distillation at 70 ℃ to obtain the multifunctional silane coupling agent with the molecular formula of (CH)3)2Si(CH2)3N(CH2)3OOCCH＝CH2(ii) a The product name is C4 for short, and the yield is about 97 percent.
Example 5:
the preparation method of the multifunctional silane coupling agent comprises the following steps:
(1)[HCl]·NH2(CH2)2cl for hydrochloric acid: preparing 10% KOH solution, adding [ HCl ]]·NH2(CH2)2Cl, stirring for 1 hour in ice-water bath; adding ethyl acetate, extracting for 3 times, and mixing organic layers; washing the organic layer with saturated sodium chloride water solution for 4 times, adding anhydrous magnesium sulfate, stirring, drying for one day and night, filtering, removing organic solvent by rotary evaporation, and vacuum drying at 30 deg.C to constant weight to obtain NH2(CH2)2Cl。
(2) 24g of gamma-chloropropyltriethoxysilane ((C) was weighed2H5O)3Si(CH2)3Cl)、8gNH2(CH2)2Adding Cl and 95g of dimethylformamide into a three-neck round-bottom flask under the protection of nitrogen, stirring, slowly heating, and reacting for 24 hours at 110 ℃; after the reaction is finished, standing still, cooling, filtering, distilling the filtrate at 70 ℃ under reduced pressure to remove residual reactants and solvent, and drying in vacuum at 30 DEG CTo constant weight, obtaining the multifunctional silane coupling agent with the molecular formula of (C)2H5O)3Si(CH2)3NH(CH2)2Cl, yield about 99%.
(3) Weighing 28g (C)2H5O)3Si(CH2)3NH(CH2)2Cl、12gCH2Adding CHCOOK and 40g of dimethylformamide into a three-neck round-bottom flask under the protection of nitrogen, adding 0.2g of ethyl triphenyl phosphonium bromide and 0.3g of 2, 6-di-tert-butyl-4-methylphenol under stirring, and heating to 125 ℃ for reacting for 1 h; after the reaction is finished, standing and cooling, filtering, distilling the filtrate at 70 ℃ under reduced pressure to remove residual reactants and solvent, and drying at 30 ℃ in vacuum to constant weight to obtain the multifunctional silane coupling agent with the molecular formula of (C)2H5O)3Si(CH2)3NH(CH2)2OOCCH＝CH2The yield was about 98%.
(4) Weighing 32g (C)2H5O)3Si(CH2)3NH(CH2)2OOCCH＝CH2、0.9g(NH4)2SO4And 83g of dimethylformamide are added into a three-neck round-bottom flask under the protection of nitrogen, the mixture is stirred, the temperature is slowly increased, and the reflux reaction is carried out for 5 hours at the temperature of 115 ℃. After the reaction is finished, the solvent and the byproduct micromolecular organic alcohol are removed by reduced pressure distillation at 70 ℃ to obtain the multifunctional silane coupling agent with the molecular formula of (C)2H5O)2Si(CH2)3N(CH2)2OOCCH＝CH2(ii) a The product name is C5 for short, and the yield is about 97 percent.
Example 6:
the preparation method of the multifunctional silane coupling agent comprises the following steps:
(1)[HCl]·NH2(CH2)2cl for hydrochloric acid: preparing 15% NaOH aqueous solution, adding [ HCl ]]·NH2(CH2)2Cl, stirring for 2 hours in ice-water bath; adding dichloromethane for extraction for 4 times, and combining organic layers; the organic layer was washed with saturated aqueous sodium chloride solution 4 times, added with anhydrous magnesium sulfate, stirred and driedFiltering at night, removing organic solvent from the filtrate by rotary evaporation, and vacuum drying at 25 deg.C to constant weight to obtain NH2(CH2)2Cl。
(2) 20g of gamma-chloropropyltrimethoxysilane ((CH)3O)3Si(CH2)3Cl)，12gNH2(CH2)2Adding Cl and 90g of toluene into a three-neck round-bottom flask under the protection of nitrogen, stirring, slowly heating, and reacting for 24 hours at 100 ℃; after the reaction is finished, standing and cooling, filtering, distilling the filtrate at 60 ℃ under reduced pressure to remove residual reactants and solvent, and drying at 25 ℃ in vacuum to constant weight to obtain the multifunctional silane coupling agent with the molecular formula of (CH)3O)3Si(CH2)3NH(CH2)2Cl, yield about 99%.
(3) Weighing 24g (CH)3O)3Si(CH2)3NH(CH2)2Cl、12gCH2Adding CHCOOK and 60g of toluene into a three-neck round-bottom flask under the protection of nitrogen, adding 0.3g of tetraphenylphosphonium chloride and 0.4g of 4- (2-aminoethyl) phenol under stirring, and heating to 110 ℃ to react for 2.5 hours; after the reaction is finished, standing and cooling, filtering, distilling the filtrate at 60 ℃ under reduced pressure to remove residual reactants and solvent, and drying at 25 ℃ in vacuum to constant weight to obtain the multifunctional silane coupling agent with the molecular formula of (CH)3O)3Si(CH2)3NH(CH2)2OOCCH＝CH2The yield was about 98%.
(4) Weighing 28g (CH)3O)3Si(CH2)3NH(CH2)2OOCCH＝CH2、1.3g(NH4)2SO4And 70g of toluene are added into a three-neck round-bottom flask under the protection of nitrogen, stirred, slowly heated and refluxed for 6 hours at the temperature of 110 ℃. After the reaction is finished, the solvent and the byproduct micromolecular organic alcohol are removed by reduced pressure distillation at 60 ℃ to obtain the multifunctional silane coupling agent with the molecular formula of (CH)3O)2Si(CH2)3N(CH2)2OOCCH＝CH2(ii) a The product name is C6 for short, and the yield is about 97 percent.
Example 7:
the preparation method of the multifunctional silane coupling agent comprises the following steps:
(1)[HCl]·NH2(CH2)2cl for hydrochloric acid: preparing ammonia water solution with the concentration of 20 percent, and adding [ HCl ]]·NH2(CH2)2Cl, stirring for 2.5 hours in ice-water bath; adding ether for extraction for 4 times, and mixing organic layers; washing the organic layer with saturated sodium chloride water solution for 3 times, adding anhydrous magnesium sulfate, stirring and drying for one day and night, filtering, removing organic solvent from the filtrate by rotary evaporation, and vacuum drying at 20 deg.C to constant weight to obtain NH2(CH2)2Cl。
(2) 18g of gamma-chloropropylmethyldimethoxysilane ((CH)3O)2CH3Si(CH2)3Cl)、20gNH2(CH2)2Cl and 110g of dimethyl sulfoxide are added into a three-neck round-bottom flask under the protection of nitrogen, stirred and slowly heated, and the mixture reacts for 12 hours at 120 ℃. After the reaction is finished, standing and cooling, filtering, distilling the filtrate at 80 ℃ under reduced pressure to remove residual reactants and solvent, and drying under vacuum at 35 ℃ to constant weight to obtain the multifunctional silane coupling agent with the molecular formula of (CH)3O)2CH3Si(CH2)3NH(CH2)2Cl, yield about 99%.
(3) Weighing 23g (CH)3O)2CH3Si(CH2)3NH(CH2)2Cl、14gCH2＝C(CH3) COOK and 60g of dimethylformamide are added into a three-neck round-bottom flask under the protection of nitrogen, 0.3g of tetrabutylammonium bromide and 0.5g of N, N' -dinaphthyl p-phenylenediamine are added under stirring, and the temperature is raised to 110 ℃ for reaction for 2.5 hours; after the reaction is finished, standing and cooling, filtering, distilling the filtrate at 70 ℃ under reduced pressure to remove residual reactants and solvent, and drying at 30 ℃ in vacuum to constant weight to obtain the multifunctional silane coupling agent with the molecular formula of (CH)3O)2CH3Si(CH2)3NH(CH2)2OOC(CH3)C＝CH2The yield was about 98%.
(4) Weighing 28g (CH)3O)2CH3Si(CH2)3NH(CH2)2OOC(CH3)C＝CH2、2g(NH4)2SO4And 70g of dimethyl sulfoxide, adding the mixture into a three-neck round-bottom flask under the protection of nitrogen, stirring, slowly heating, and carrying out reflux reaction at 125 ℃ for 3 hours. After the reaction is finished, the solvent and the byproduct micromolecular organic alcohol are removed by reduced pressure distillation at the temperature of 80 ℃ to obtain the multifunctional silane coupling agent with the molecular formula of (CH)3O)CH3Si(CH2)3N(CH2)2OOC(CH3)C＝CH2(ii) a The product name is C7 for short, and the yield is about 97 percent.
Example 8:
the preparation method of the multifunctional silane coupling agent comprises the following steps:
(1)[HCl]·NH2(CH2)2cl for hydrochloric acid: k with the preparation concentration of 30%2CO3Solution, adding [ HCl ]]·NH2(CH2)2Cl, stirring for 2 hours in ice-water bath; adding chloroform for extraction for 3 times, and combining organic layers; washing the organic layer with saturated sodium chloride water solution for 3 times, adding anhydrous magnesium sulfate, stirring and drying for one day and night, filtering, removing organic solvent from the filtrate by rotary evaporation, and vacuum drying at 30 deg.C to constant weight to obtain NH2(CH2)2Cl。
(2) 16g of gamma-chloropropylmethoxydimethylsilane ((CH) are weighed out3O)(CH3)2Si(CH2)3Cl)、30gNH2(CH2)2Cl and 95g of dimethylformamide are added into a three-neck round-bottom flask under the protection of nitrogen, stirred and slowly heated to react for 24 hours at 110 ℃. After the reaction is finished, standing and cooling, filtering, distilling the filtrate at 70 ℃ under reduced pressure to remove residual reactants and solvent, and drying under vacuum at 30 ℃ to constant weight to obtain the multifunctional silane coupling agent with the molecular formula of (CH)3O)(CH3)2Si(CH2)3NH(CH2)2Cl, yield about 99%.
(3) Weighing 21g (CH)3O)(CH3)2Si(CH2)3NH(CH2)2Cl、15gCH2＝C(CH3) COOK and 50g of dimethylformamide are added into a three-neck round-bottom flask under the protection of nitrogen, 0.4g of tetrabutylammonium iodide and 0.6g of 4- (2-aminoethyl) phenol are added under stirring, and the temperature is raised to 110 ℃ for reaction for 2.5 hours; after the reaction is finished, standing and cooling, filtering, distilling the filtrate at 70 ℃ under reduced pressure to remove residual reactants and solvent, and drying at 30 ℃ in vacuum to constant weight to obtain the multifunctional silane coupling agent with the molecular formula of (CH)3O)(CH3)2Si(CH2)3NH(CH2)2OOC(CH3)C＝CH2The yield was about 98%.
(4) Weighing 26g (CH)3O)(CH3)2Si(CH2)3NH(CH2)2OOC(CH3)C＝CH2、2.6g(NH4)2SO4And 65g of dimethylformamide are added into a three-neck round-bottom flask under the protection of nitrogen, stirred, slowly heated and refluxed for 4 hours at 120 ℃. After the reaction is finished, the solvent and the byproduct micromolecular organic alcohol are removed by reduced pressure distillation at 70 ℃ to obtain the multifunctional silane coupling agent with the molecular formula of (CH)3)2Si(CH2)3N(CH2)2OOC(CH3)C＝CH2(ii) a The product name is C8 for short, and the yield is about 97 percent.
Application example:
the compound preparation was carried out according to the formulation shown in table 1, and both # 1 and # 2 were carried out according to a conventional mixing process.
TABLE 1 basic formulation of flame retardant natural rubber composites
The rubber compound prepared according to the formula shown in Table 1 is vulcanized for 15min at 150 ℃, the mechanical properties of the vulcanized rubber are shown in Table 2, the pressure change and resilience properties are shown in Table 3, the heat generation properties are shown in Table 4, the creep properties are shown in Table 5, and the flame retardant properties are shown in Table 6. As shown in Table 2, the multifunctional silane coupling agent C1 has a good reinforcing effect on natural rubber compounds containing a large amount of flame retardants, and can effectively improve the tensile strength and the stress at definite elongation of vulcanized rubber.
TABLE 2 mechanical Properties of flame-retardant Natural rubber vulcanizates
TABLE 3 pressure Change and Resilience Properties of flame-retardant Natural rubber vulcanizate
As can be seen from Table 3, the addition of the multifunctional silane coupling agent C1 significantly reduced the strain of the natural rubber compound containing a large amount of flame retardant and increased the rebound thereof.
TABLE 4 Heat buildup Properties of flame retardant Natural rubber vulcanizates
As can be seen from Table 4, after the multifunctional silane coupling agent C1 is added to the natural rubber compound containing a large amount of flame retardant, the compression fatigue temperature rise and Tan delta (Tan delta: also called loss factor, which is the tangent of the phase difference angle between strain and stress cycle of the viscoelastic material under the action of an alternating force field and is also equal to the ratio of loss modulus to storage modulus of the material) at 23 ℃ and 60 ℃ are all significantly reduced, which indicates that the heat buildup property of the vulcanized rubber is significantly improved.
TABLE 5 creep properties of flame retardant Natural rubber vulcanizates
As can be seen from Table 5, the addition of the multifunctional silane coupling agent C1 to the natural rubber compound containing a large amount of flame retardant significantly reduced the compressive creep amount and compressive creep increment, indicating that the creep property of the vulcanized rubber was further significantly improved.
TABLE 6 flame retardance of flame retarded Natural rubber vulcanizates
As can be seen from Table 6, the flame retardant properties of the compound still meet the requirements by adding the multifunctional silane coupling agent C1.
As can be seen from the above implementation and comparative examples, the multifunctional silane coupling agent containing cyclic silazoyl and (meth) acryloyloxyalkyl functional groups provided by the invention has a good reinforcing effect on natural rubber compounds containing a large amount of hydrated metal oxides, the compounds do not need to be heated at high temperature and have high coupling efficiency, the flame retardance is maintained, the tensile strength and the stress at definite elongation are effectively improved, the compression permanent deformation is remarkably reduced, and the heat generation performance and the creep performance are remarkably improved.
The foregoing is considered as illustrative of the preferred embodiments of the invention and is not to be construed as limiting the invention in any way. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention should fall within the protection scope of the technical scheme of the present invention, unless the technical spirit of the present invention departs from the content of the technical scheme of the present invention.
Claims (9)
1. The multifunctional silane coupling agent is characterized in that the molecular structure of the silane coupling agent simultaneously contains a cyclic silicon nitrogen-based functional group and a (meth) acryloyloxy hydrocarbon-based functional group, and the (meth) acryloyloxy hydrocarbon-based functional group comprises an acryloyloxy hydrocarbon-based and/or a methacryloyloxyhydrocarbon-based.
2. The multifunctional silane coupling agent of claim 1, wherein the cyclic silazane-based functional group comprises one or more of a cyclic dialkoxysilazenyl group, a cyclic alkylalkoxysilazane group, or a cyclic dialkoxysilazenyl group.
3. The multifunctional silane coupling agent according to claim 1 or 2, wherein the molecular structural formula of the multifunctional silane coupling agent is any one of the following general formulas:
wherein x is 0, 1 or 2, R1、R2Are identical or different straight-chain or branched alkyl radicals of 1 to 10 carbon atoms, R3Is a straight or branched alkyl group of 1 to 15 carbon atoms, R4Is a straight or branched alkyl group of 1 to 18 carbon atoms, R5Is methyl or hydrogen.
4. The multifunctional silane coupling agent of claim 3, wherein R is1、R2Are the same or different C1-C3 straight chain or branched chain alkyl groups, R3Is C1-C3 straight chain or branched chain alkyl, R4Is C1-C3 straight chain or branched chain alkyl.
5. The multifunctional silane coupling agent according to claim 4, wherein the multifunctional silane coupling agent has the formula (C)2H5O)2Si(CH2)3N(CH2)3OOC(CH3)C＝CH2、(CH3O)2Si(CH2)3N(CH2)3OOC(CH3)C＝CH2、(CH3O)CH3Si(CH2)3N(CH2)3OOCCH＝CH2、(CH3)2Si(CH2)3N(CH2)3OOCCH＝CH2、(C2H5O)2Si(CH2)3N(CH2)2OOCCH＝CH2、(CH3O)2Si(CH2)3N(CH2)2OOCCH＝CH2、(CH3O)CH3Si(CH2)3N(CH2)2OOC(CH3)C＝CH2Or (CH)3)2Si(CH2)3N(CH2)2OOC(CH3)C＝CH2。
6. A method for preparing the multifunctional silane coupling agent according to any one of claims 3 to 5, wherein the multifunctional silane coupling agent is prepared byThe method comprises the following steps: the molecular structural formula is (R)1O)3-xSiR2 xR3The compound and the molecular structural formula of X are NH2R4The compound of X is subjected to amination reaction to prepare (R)1O)3-xSiR2 xR3NHR4X, will (R)1O)3-xSiR2 xR3NHR4X and the molecular structural formula is CH2＝CR5COOM compound is subjected to desalting condensation reaction under the action of a phase transfer catalyst to prepare (R)1O)3-xSiR2 xR3NHR4OOCR5C＝CH2Will (R)1O)3-xSiR2 xR3NHR4OOCR5C＝CH2Carrying out dealcoholization reaction under the action of ammonium salt to obtain the multifunctional silane coupling agent: (R)1O)2-xSiR2 xR3NR4OOCR5C＝CH2(ii) a Wherein X is 0, 1 or 2, X is Cl, Br or I, M is sodium ion or potassium ion, R is1、R2Are identical or different straight-chain or branched alkyl radicals of 1 to 10 carbon atoms, R3Is a straight or branched alkyl group of 1 to 15 carbon atoms, R4Is a straight or branched alkyl group of 1 to 18 carbon atoms, R5Is methyl or hydrogen.
7. The method for preparing a multifunctional silane coupling agent according to claim 6, wherein the molecular formula of [ HCl ] is first prepared]·NH2R4The compound of X is subjected to desalting and acid treatment in an alkali solution to obtain a compound with a molecular structural formula of NH2R4A compound of X.
8. Use of the multifunctional silane coupling agent of any one of claims 1 to 5 or the multifunctional silane coupling agent prepared according to any one of claims 6 to 7 in a flame retardant natural rubber composite material, wherein the flame retardant natural rubber composite material is a natural rubber to which an inorganic flame retardant is added, the natural rubber being a hydrated metal oxide.
9. Use according to claim 8, wherein the hydrated metal oxide comprises aluminium hydroxide or magnesium hydroxide.
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