CN112210068A - Moisture-curable modified polysiloxane, and preparation method and application thereof - Google Patents

Moisture-curable modified polysiloxane, and preparation method and application thereof Download PDF

Info

Publication number
CN112210068A
CN112210068A CN202011114396.4A CN202011114396A CN112210068A CN 112210068 A CN112210068 A CN 112210068A CN 202011114396 A CN202011114396 A CN 202011114396A CN 112210068 A CN112210068 A CN 112210068A
Authority
CN
China
Prior art keywords
alkyl
moisture
modified polysiloxane
polysiloxane
aryl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011114396.4A
Other languages
Chinese (zh)
Inventor
侯浩波
纪建业
叶非华
张鹏举
李银生
江俊锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhaoqing Wuda Institute Of Environmental Technology
Original Assignee
Zhaoqing Wuda Institute Of Environmental Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhaoqing Wuda Institute Of Environmental Technology filed Critical Zhaoqing Wuda Institute Of Environmental Technology
Priority to CN202011114396.4A priority Critical patent/CN112210068A/en
Publication of CN112210068A publication Critical patent/CN112210068A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/778—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur silicon
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • 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
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin compounds
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

The invention relates to moisture-curable modified polysiloxane, a preparation method and application thereof. The modified polysiloxane has a single linear structure, the end group is siloxy, the modified polysiloxane can be cured by moisture at room temperature, the viscosity before and after curing is stable, and the modified polysiloxane has the advantages of mild curing conditions, no limitation of curing depth and deep curing. The modified polysiloxane is applied to preparing room temperature vulcanized silicone rubber, can fundamentally solve the problem of viscosity peak in the curing process of the traditional polysiloxane, improves the storage stability of the product, ensures the normal curing of the product, and has excellent performance and good application value.

Description

Moisture-curable modified polysiloxane, and preparation method and application thereof
Technical Field
The invention relates to modified polysiloxane, in particular to moisture-curable modified polysiloxane, a preparation method thereof and application of alkoxy polysiloxane in a silicone rubber composition, and belongs to the field of organic silicon adhesives.
Background
The single-component room temperature moisture vulcanized silicone rubber product is convenient to apply, less affected by temperature in the vulcanization process and good in adhesion, and is widely applied to the fields of buildings, electronics and electrics, aerospace, automobile accessories and photovoltaic cells. Room temperature vulcanizing silicone rubbers generally consist of a hydroxyl terminated polysiloxane, an alkoxysilane crosslinking agent, a filler, and an organometallic catalyst. In the process of mixing preparation, a transient crosslinking process can occur, which causes the viscosity of the system to be increased rapidly, even the phenomenon of gel agglomeration, called as viscosity peak, needs to be acted by high shear force and placed for a period of time to reduce the viscosity, and seriously affects the processing safety and the production efficiency. In addition, in the storage process, the silicon hydroxyl and the cross-linking agent react to separate out alcohol micromolecules, and the small molecular alcohol substances can react with polysiloxane in the matrix to generate low-activity monoalkoxyl polymers, so that the system cannot be solidified into a film in the application process, and the application effect and the storage stability of the product are influenced.
Chinese patent (CN201310395394.0) and Chinese patent (CN201711371842.8) disclose a method for preparing alkoxy-terminated polysiloxane by condensation reaction of hydroxyl-terminated polysiloxane and micromolecular silane containing 2-4 alkoxy. The method has the defects that the system is easy to leave small alkoxy silane molecules, and the small alkoxy silane molecules are equivalent to a crosslinking agent in the system and influence the curing performance of the product in the later film forming process. In addition, because the activities of the alkoxy micromolecule reactive groups are the same, the system is easy to crosslink and gel in the end capping process, and the preparation effect and the product performance are influenced. Also, to ensure consistency of polymer viscosity before and after capping, the capped polymer is generally not of a single linear structure. Meanwhile, when the alkoxy-terminated polysiloxane is prepared by the method, the reaction process is often carried out under the conditions of adding a solvent and high shear in order to avoid serious crosslinking gel of the system, the process is complex, and the reaction is difficult to control. Therefore, the preparation method of the alkoxy-terminated polysiloxane polymer with a single product structure and the room temperature vulcanized silicone rubber composition thereof has very important significance, and the reaction process is simple, the process is easy to control, the system gel problem is not required to be considered.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a modified polysiloxane which has a single linear structure and a silane oxygen group as a terminal group, can be cured by moisture at room temperature, has stable viscosity before and after curing, and has the advantages of mild curing conditions, no curing depth limitation and deep curing.
It is a second object of the present invention to provide a process for producing a modified polysiloxane with a simple process and at low cost.
The third purpose of the invention is to provide an application of the modified polysiloxane, the modified polysiloxane is applied to the preparation of room temperature vulcanized silicone rubber, the problem of viscosity peak in the curing process of the traditional polysiloxane can be fundamentally solved, the storage stability of the product is improved, the normal curing of the product is ensured, and the prepared silicone rubber composition has excellent performance and good application value.
In order to achieve the above technical object, the present invention provides a moisture-curable modified polysiloxane having a structure of formula 1:
Figure BDA0002729759710000021
wherein,
R1is aryl, alkyl or arylalkyl;
R2is C1～C8An aliphatic hydrocarbon group of (1);
x and y are both integers of 2-5; n is a natural integer greater than 1; z is an integer of 1-8; j is 0, 1 or 2.
As a preferred embodiment, R1When aryl, aryl is phenyl, naphthyl, or contains C1～C10Alkyl or C1～C10Phenyl of alkoxy; wherein, C on the benzene ring1～C10Alkyl or C1～C10The position of the alkoxy group on the benzene ring is not limited, and C1～C10The alkyl group may be a straight-chain alkyl group such as methyl, propyl, octyl, etc., and when the number of carbon atoms of the alkyl group exceeds 3, the alkyl group may be a branched alkyl group such as isobutyl, etc.; c1～C10The alkoxy group may be a linear alkoxy group such as methoxy, ethoxy, and the like.
As a preferred embodiment, R1When it is an alkyl group, the alkyl group is C1～C10An alkyl group; and C1～C10The alkyl group may be a straight-chain alkyl group such as methyl, propyl, octyl, etc., and when the number of carbon atoms of the alkyl group exceeds 3, the alkyl group may be a branched alkyl group such as isobutyl, etc.
R1Is arylalkyl, which is C having an aryl substituent1～C10Alkyl, wherein the aryl substituent is phenyl, naphthyl, or contains C1～C10Alkyl or C1～C10Phenyl of alkoxy; said compound containing C1～C10Alkyl or C1～C10In the phenyl group of the alkoxy group, C on the benzene ring1～C10Alkyl or C1～C10The position of the alkoxy group on the benzene ring is not limited, and C1～C10The alkyl group may be a straight-chain alkyl group such as methyl, propyl, octyl, etc., and when the number of carbon atoms of the alkyl group exceeds 3, the alkyl group may be a branched alkyl group such as isobutyl, etc.; c1～C10The alkoxy group may be a linear alkoxy group such as methoxy, ethoxy, and the like.
The invention also provides a preparation method of the moisture-curable modified polysiloxane, which is obtained by addition reaction of the double-end hydroxyl alkyl polysiloxane and the isocyanato alkoxy silane;
the double-terminal hydroxyl alkyl polysiloxane has a structure shown in a formula 2:
Figure BDA0002729759710000031
the isocyanatoalkoxysilane has the structure of formula 3:
Figure BDA0002729759710000032
wherein,
R1is aryl, alkyl or arylalkyl;
R2is C1～C8An aliphatic hydrocarbon group of (1);
x and y are both integers of 2-5; n is a natural integer greater than 1; z is an integer of 1-8; j is 0, 1 or 2.
As a preferred embodiment, R1When aryl, aryl is phenyl, naphthyl, or contains C1～C10Alkyl or C1～C10Phenyl of alkoxy; r1When it is an alkyl group, the alkyl group is C1～C10An alkyl group; r1Is arylalkyl, which is C having an aryl substituent1～C10Alkyl, wherein aryl is phenyl, naphthyl, or contains C1～C10Alkyl or C1～C10Phenyl of alkoxy.
As a preferable scheme, the double-end hydroxyl alkyl polysiloxane and the isocyanato alkoxy silane react for 2-8 hours at the temperature of 40-80 ℃ under the action of a catalyst.
As a preferable scheme, the reaction ratio of the double-end hydroxyl alkyl polysiloxane and the isocyanato alkoxy silane is measured according to the molar ratio of hydroxyl to isocyanate of 1: 1.0-3.0.
As a preferable mode, the catalyst is at least one of zirconium chelate (e.g., zirconium acetylacetonate, beta-diketonate, etc.), tertiary amine catalyst (e.g., triethylamine, triethylenediamine, tetramethylbutanediamine, aminoalcohol, etc.), organotin catalyst (e.g., dibutyltin dilaurate, dibutyltin diacetate, stannous octoate, tin chloride, stannous chloride, butyltin acetate, etc.), N-methylmorpholine, triphenylphosphine, dinonylnaphthalenedisulfonic acid, bismuth carboxylate, zinc octoate, cobalt octoate, manganese acetylacetonate, tetramethylguanidine, N-N-butyltetramethylguanidine, aminal, amidine salt, phenoxide, organotitanium, and titanium complex catalyst.
Preferably, the amount of the catalyst is 0.0005 to 0.05 mass% based on the weight of the hydrocarbyl-terminated polysiloxane.
As a preferred embodiment, the viscosity of the both-terminal hydroxyalkyl polysiloxane is in the range of
100-500000 cst. Preferably 1000 to 30000cst
The invention also provides application of the moisture-curable modified polysiloxane in preparation of room-temperature vulcanized silicone rubber.
As a preferred technical scheme, the room temperature vulcanized silicone rubber comprises the following raw materials in parts by mass: 20-80 parts of modified polysiloxane; 0-50 parts of a filler; 0.1-4 parts of a catalyst; 0.1-4 parts of a tackifier; 0.1-3 parts of color master batch. Further preferably, the room temperature vulcanized silicone rubber comprises the following raw materials in parts by mass:
30-80 parts of modified polysiloxane; 20-40 parts of a filler; 0.5-4 parts of a catalyst; 0.5-3 parts of a tackifier; 0.4-1 part of color master batch.
As a preferred embodiment, the filler is at least one of calcium carbonate, graphene oxide, fumed silica, precipitated silica, alumina, zinc oxide, silicone resin, and aluminum hydroxide.
In a preferred embodiment, the catalyst is at least one of dibutyltin dilaurate, dibutyltin diacetate, stannous octoate, stannic chloride, stannous chloride, butyltin acetate, tetraisopropyl titanate, n-butyl titanate, tetra-t-butyl titanate, tetraisobutyl titanate, and titanium diisopropoxydiethylacetoacetate.
As a preferable scheme, the tackifier is at least one of gamma-methacryloxypropyltrimethoxysilane, aminopropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, isocyanate trimethoxysilane, isocyanate triethoxysilane, phenylaminotrimethoxysilane, phenylaminotriethoxysilane, diethoxymethylsilane, dimethylethoxysilane, triethoxysilane, dimethylmethoxysilane, methyldimethoxysilane, trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and mercaptopropyltrimethoxysilane.
As a preferable scheme, the color master is at least one of silica gel color master, cadmium red, cadmium yellow, titanium dioxide, carbon black, iron oxide red and iron oxide yellow.
The modified polysiloxane is prepared by the following method: mixing the bi-terminal alkyl hydroxyl polysiloxane and isocyanato alkoxy silane according to the molar ratio of hydroxyl to isocyanato of 1: 1-3, adding a catalyst, stirring and mixing under a vacuum condition, wherein the reaction temperature is 40-80 ℃, and the reaction time is 2-8 hours, so as to obtain the moisture curing modified polysiloxane polymer.
The invention also provides a preparation method of the room-temperature moisture-curable silicone rubber, which comprises the following steps:
step 1): mixing polysiloxane with alkyl hydroxyl at two ends and isocyanato-alkoxy silane according to the molar ratio of 1: 1-3, adding a certain amount of catalyst, stirring and mixing under a vacuum condition, wherein the reaction temperature is 40-80 ℃, and the reaction time is 2-8 hours, so as to prepare the moisture-curable polysiloxane polymer.
Step 2): the dry moisture curing polysiloxane polymer, the filler, the catalyst, the tackifier and the color master are mechanically mixed and sealed according to a certain proportion under the vacuum sealing condition, and a single-component room-temperature moisture curing silicone rubber product can be obtained.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the modified polysiloxane has a single linear structure, the end group is siloxy, the modified polysiloxane can be cured by moisture at room temperature, the viscosity before and after curing is stable, the modified polysiloxane has the advantages of mild curing conditions, no limitation of curing depth and deep curing, and the problems that the production efficiency is influenced and the production safety is influenced by the viscosity peak in the traditional process of curing the hydroxyl-terminated polysiloxane mixed glue by moisture at room temperature are effectively solved.
The modified polysiloxane provided by the invention has good bonding performance when being used for curing vulcanized silicone rubber, and can be widely applied to the fields of electronic bonding, packaging, building sealing, photovoltaic cells, automobile parts, 3D printing and the like.
The modified polysiloxane of the invention has simple preparation steps and low cost, and is beneficial to industrial large-scale production.
Drawings
FIG. 1 is an infrared comparison of the product of the hydroxyalkyl polysiloxane and trimethoxy terminated polysiloxane of example 1.
Detailed Description
The present invention is further illustrated by the following detailed description and examples, but the scope of the claims is not limited by the specific examples.
Example 1
100g of 1000cst (hydroxyl content is 6.0mmol/100g) hydroxyalkyl polysiloxane, 1.3g of isocyanatopropyl trimethoxy silane and 1 part of n-butyl titanate are added into a reaction kettle provided with a thermometer, a stirrer and a snakelike condensation tube, and stirred and reacted for 4 hours in a vacuum state to obtain a trimethoxy end-capped polysiloxane product with the viscosity of 1200 cst.
The infrared comparison of the hydroxyalkyl polysiloxane with trimethoxy terminated polysiloxane product is shown in FIG. 1. In the hydroxyalkyl polysiloxanes, the silyl radical (Si-CH)3) The peak of the stretching vibration of the diaphragm appears at 2964 cm-1And 2906 cm-1At least one of (1) and (b); the symmetric deformation vibration peak appears at 1261cm-1And 1411cm-1At least one of (1) and (b); 2848cm-1The absorption at (A) is due to methylene (CH)2) Characteristic peak of (a); 1020cm-1And 1099 cm-1The characteristic absorption of (A) is the antisymmetric stretching vibration absorption of silicon oxygen (Si-O-Si) bond, and the characteristic peak of hydroxyl (OH) appears at 3693cm-1To (3). The modified polysiloxane was predominantly expressed at 3693cm in comparison with the FT-IR infrared spectrum of the hydroxyhydrocarbyl polysiloxane-1The characteristic peak of hydroxyl (-OH) group had completely disappeared, and the characteristic peak of NH group in urethane group was 3370cm-1It is shown that hydroxyl groups in the hydroxyalkyl polysiloxane molecule completely undergo a hydroxyl esterification reaction with isocyanate groups, and isocyanatoalkoxysilane has been successfully introduced into the molecular backbone.
Example 2
100g of 5000cst (hydroxyl content is 3.0mmol/100g) hydroxyalkyl polysiloxane, 0.9g of isocyanatopropyl triethoxysilane and 1 part of n-butyl titanate are added into a reaction kettle provided with a thermometer, a stirrer and a snakelike condensing tube, and stirred and reacted for 4 hours in a vacuum state to obtain a triethoxy terminated polysiloxane product with the viscosity of 6000 cst.
Example 3
20000cst (hydroxyl content 1.0mmol/100g) of hydroxyalkyl polysiloxane 100g, isocyanatopropyl diethoxysilane 0.2g and n-butyl titanate 1 part are added into a reaction kettle provided with a thermometer, a stirrer and a serpentine condenser, and stirred and reacted for 4 hours in a vacuum state to obtain dimethoxy terminated polysiloxane with the viscosity of 23000 cst.
Example 4
According to parts by weight, 50 parts of polysiloxane prepared in example 1, 15 parts of fumed silica, 0.5 part of dibutyltin dilaurate, 2 parts of aminoethyl aminopropyl triethoxysilane and 1 part of carbon black are uniformly stirred.
Example 5
By weight, 50 parts of polysiloxane prepared in example 2, 15 parts of calcium carbonate, 0.5 part of dibutyltin dilaurate, 2 parts of aminoethyl aminopropyl triethoxysilane and 1 part of carbon black are uniformly stirred.
Example 6
50 parts of polysiloxane prepared in example 3, 15 parts of calcium carbonate, 0.5 part of dibutyltin dilaurate, 2 parts of aminoethyl aminopropyl triethoxysilane and 1 part of carbon black are taken by weight parts and stirred uniformly.
Example 7
According to parts by weight, 25 parts of polysiloxane prepared in example 2, 25 parts of polysiloxane prepared in example 3, 15 parts of fumed silica, 0.5 part of dibutyltin dilaurate, 2 parts of aminoethyl aminopropyl triethoxysilane and 1 part of carbon black are uniformly stirred.
Comparative example
According to parts by weight, 50 parts of common 5000cst hydroxyl-terminated polysiloxane, 15 parts of fumed silica, 0.5 part of dibutyltin dilaurate, 2 parts of aminoethyl aminopropyl triethoxysilane and 1 part of carbon black are uniformly stirred.
The properties of the moisture-curing polysiloxanes of examples 4-7 and comparative examples are shown in the following table:
Figure BDA0002729759710000071
as can be seen from the above table, the modified silicone rubber prepared by using the alkoxy-terminated polysiloxane can be completely cured, and after 7 days of curing time, the comprehensive performance is obviously superior to that of a moisture-cured silicone rubber product with the same viscosity.
The above-mentioned embodiments only express the implementation mode of the present invention, and the detailed description is not to be understood as the limitation of the patent scope of the present invention. It is pointed out that several variations and modifications can be made by a person skilled in the art without departing from the inventive concept, which falls within the scope of the invention. Therefore, the protection scope of the present invention should be subject to the appended claims.

Claims (10)

1. A moisture-curable modified polysiloxane characterized by: has the structure of formula 1:
Figure FDA0002729759700000011
wherein,
R1is aryl, alkyl or arylalkyl;
R2is C1～C8An aliphatic hydrocarbon group of (1);
x and y are both integers of 2-5; n is a natural integer greater than 1; z is an integer of 1-8; j is 0, 1 or 2.
2. The moisture-curable modified polysiloxane according to claim 1, characterized in that:
R1when aryl, aryl is phenyl, naphthyl, or contains C1～C10Alkyl or C1～C10Phenyl of alkoxy;
R1when it is an alkyl group, the alkyl group is C1～C10An alkyl group;
R1is arylalkyl, which is C having an aryl substituent1～C10Alkyl, wherein the aryl substituent is phenyl, naphthyl, or contains C1～C10Alkyl or C1～C10Phenyl of alkoxy.
3. A process for producing a moisture-curable modified polysiloxane according to claim 1 or 2, characterized in that: carrying out addition reaction on double-end hydroxyl alkyl polysiloxane and isocyanato alkoxy silane to obtain the product;
the double-terminal hydroxyl alkyl polysiloxane has a structure shown in a formula 2:
Figure FDA0002729759700000012
the isocyanatoalkoxysilane has the structure of formula 3:
Figure FDA0002729759700000013
wherein,
R1is aryl, alkyl or arylalkyl;
R2is C1～C8An aliphatic hydrocarbon group of (1);
x and y are both integers of 2-5; n is a natural integer greater than 1; z is an integer of 1-8; j is 0, 1 or 2.
4. The method of producing a moisture-curable modified polysiloxane according to claim 3, characterized in that:
R1when aryl, aryl is phenyl, naphthyl, or contains C1～C10Alkyl or C1～C10Phenyl of alkoxy;
R1when it is an alkyl group, the alkyl group is C1～C10An alkyl group;
R1is arylalkyl, which is C having an aryl substituent1～C10Alkyl, wherein aryl is phenyl, naphthyl, or contains C1～C10Alkyl or C1～C10Phenyl of alkoxy.
5. The method of producing a moisture-curable modified polysiloxane according to claim 3, characterized in that: the double-end hydroxyl alkyl polysiloxane and isocyanato alkoxy silane react for 2-8 hours at the temperature of 40-80 ℃ under the action of a catalyst.
6. The method of producing a moisture-curable modified polysiloxane according to claim 5, characterized in that: the reaction ratio of the double-end hydroxyl alkyl polysiloxane and the isocyanato alkoxy silane is measured according to the molar ratio of hydroxyl to isocyanato of 1: 1.0-3.0.
7. The method of producing a moisture-curable modified polysiloxane according to claim 5, characterized in that: the catalyst is at least one of zirconium chelate, tertiary amine catalyst, organic tin catalyst, N-methylmorpholine, triphenylphosphine, dinonyl naphthalene disulfonic acid, bismuth carboxylate, zinc octoate, cobalt octoate, manganese acetylacetonate, tetramethylguanidine, N-N-butyl tetramethylguanidine, aminal, amidine salt, phenolate, organic titanium and titanium complex catalyst;
the amount of the catalyst is 0.0005-0.05 times of the mass of the double-end alkyl polysiloxane;
the viscosity range of the double-end hydroxyl alkyl polysiloxane is 100-500000 cst.
8. Use of a moisture-curable modified polysiloxane according to claim 1, characterized in that: the preparation method is applied to the preparation of room temperature vulcanization type silicon rubber.
9. Use of a moisture-curable modified polysiloxane according to claim 8, characterized in that: the room temperature vulcanized silicone rubber comprises the following raw materials in parts by mass:
20-80 parts of modified polysiloxane;
0-50 parts of a filler;
0.1-4 parts of a catalyst;
0.1-4 parts of a tackifier;
0.1-3 parts of color master batch.
10. Use of a moisture-curable modified polysiloxane according to claim 9, characterized in that: the filler is at least one of calcium carbonate, graphene oxide, fumed silica, precipitated silica, aluminum oxide, zinc oxide, silicone resin and aluminum hydroxide;
the catalyst is at least one of dibutyltin dilaurate, dibutyltin diacetate, stannous octoate, tin chloride, stannous chloride, butyltin acetate, tetraisopropyl titanate, n-butyl titanate, tetra-tert-butyl titanate, tetraisobutyl titanate and titanium diisopropoxydiethylacetoacetate;
the tackifier is at least one of gamma-methacryloxypropyltrimethoxysilane, aminopropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, isocyanate trimethoxysilane, isocyanate triethoxysilane, phenylaminotrimethoxysilane, phenylaminotriethoxysilane, diethoxymethylsilane, dimethylethoxysilane, triethoxysilane, dimethylmethoxysilane, methyldimethoxysilane, trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and mercaptopropyltrimethoxysilane;
the color master is at least one of silica gel color master, cadmium red, cadmium yellow, titanium dioxide, carbon black, iron oxide red and iron oxide yellow.
CN202011114396.4A 2020-10-19 2020-10-19 Moisture-curable modified polysiloxane, and preparation method and application thereof Pending CN112210068A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011114396.4A CN112210068A (en) 2020-10-19 2020-10-19 Moisture-curable modified polysiloxane, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011114396.4A CN112210068A (en) 2020-10-19 2020-10-19 Moisture-curable modified polysiloxane, and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN112210068A true CN112210068A (en) 2021-01-12

Family

ID=74055703

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011114396.4A Pending CN112210068A (en) 2020-10-19 2020-10-19 Moisture-curable modified polysiloxane, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112210068A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113234417A (en) * 2021-05-08 2021-08-10 东莞新能德科技有限公司 Elastic glue, preparation method thereof and battery comprising elastic glue

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120251832A1 (en) * 2011-03-31 2012-10-04 Momentive Performance Materials Inc. Moisture Curable Silylated Polymer Compositions With Improved Adhesion to Concrete
US20150031806A1 (en) * 2013-07-24 2015-01-29 Momentive Performance Materials Inc. Moisture curable compositions with enhanced elongation and tear strentgh properties
CN105367799A (en) * 2015-12-18 2016-03-02 北京天山新材料技术有限公司 Modified polysiloxane room temperature vulcanized silicone rubber
CN105601932A (en) * 2016-01-20 2016-05-25 北京天山新材料技术有限公司 Dual-curing type modified silicone rubber and preparation method thereof
CN111748090A (en) * 2019-03-29 2020-10-09 比亚迪股份有限公司 Surface modifier, heat-conducting encapsulating composite material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120251832A1 (en) * 2011-03-31 2012-10-04 Momentive Performance Materials Inc. Moisture Curable Silylated Polymer Compositions With Improved Adhesion to Concrete
US20150031806A1 (en) * 2013-07-24 2015-01-29 Momentive Performance Materials Inc. Moisture curable compositions with enhanced elongation and tear strentgh properties
CN105367799A (en) * 2015-12-18 2016-03-02 北京天山新材料技术有限公司 Modified polysiloxane room temperature vulcanized silicone rubber
CN105601932A (en) * 2016-01-20 2016-05-25 北京天山新材料技术有限公司 Dual-curing type modified silicone rubber and preparation method thereof
CN111748090A (en) * 2019-03-29 2020-10-09 比亚迪股份有限公司 Surface modifier, heat-conducting encapsulating composite material and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113234417A (en) * 2021-05-08 2021-08-10 东莞新能德科技有限公司 Elastic glue, preparation method thereof and battery comprising elastic glue

Similar Documents

Publication Publication Date Title
CN1138808C (en) Process for producing prepolymers which cure to improved sealants, and products formed thereby
CN101326255B (en) Continuous process for production of silicone pressure sensitive adhesives
KR100194303B1 (en) Improved Room Temperature Curable Silicone Composition
KR101490785B1 (en) Curable silicon-containing compositions possessing high translucency
CN1861688B (en) Room temperature-curable organopolysiloxane compositions
CN110305621A (en) A kind of dealcoholized cold curing organosilicon sealant and preparation method thereof
TW383320B (en) Moisture curable compositions
JP2004536957A (en) Alkoxy crosslinkable one-component moisture curable material
CN101679749A (en) Rapid deep-section cure silicone compositions
CN111183186B (en) Method for producing room-temperature-curable organopolysiloxane composition, and article
US20150240057A1 (en) Room-temperature-curable polyorganosiloxane composition
CN104087228A (en) Low-modulus silicyl-terminated modified polyether sealant and preparation method thereof
WO2013037105A1 (en) Filled silicone composition, preparation and uses thereof
CN114773379B (en) Modified siloxane, heat-resistant silicone structural sealant and preparation method thereof
CN114989764B (en) Silane modified polyether sealant for interior decoration and preparation method and application thereof
CN112210068A (en) Moisture-curable modified polysiloxane, and preparation method and application thereof
CN115427510B (en) Room temperature curable organopolysiloxane composition and article
CN112210341B (en) Double-vulcanization system building sealant and preparation method thereof
EP4180488A1 (en) Two-component type room temperature fast-curing organopolysiloxane composition, cured product thereof and article
JP2008266521A (en) Moisture-curable resin composition
CN112094434A (en) Preparation method and application of silicon-alkoxy-containing borosilicate siloxane modified white carbon black
JP2811140B2 (en) Room temperature curable composition
CN113789057A (en) One-pack type modified liquid silicone rubber, composition for forming same, and application thereof
CN112239643A (en) Neutral transparent silicone adhesive and preparation method thereof
CN115305049B (en) High-stability methanol-removing type silicone sealant and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20210112