CN109293912B - Polyether with controlled silicon content and preparation method and application thereof - Google Patents

Polyether with controlled silicon content and preparation method and application thereof Download PDF

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CN109293912B
CN109293912B CN201811108339.8A CN201811108339A CN109293912B CN 109293912 B CN109293912 B CN 109293912B CN 201811108339 A CN201811108339 A CN 201811108339A CN 109293912 B CN109293912 B CN 109293912B
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polyether
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catalyst
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CN109293912A (en
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殷玲
鞠昌迅
秦承群
王明永
叶天
刘洋
李付国
石正阳
黎源
华卫琦
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Wanhua Chemical Group Co Ltd
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    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides

Abstract

The invention discloses modified polyether with controlled silicon content, a preparation method thereof and application of the modified polyether as sealant. Monohydric alcohol or dihydric alcohol is used as an initiator, an epoxy structural monomer containing unsaturated bonds and a conventional polyether synthetic monomer are adopted to firstly synthesize a compound with one or more double bonds, and a silicon-modified polyether with controllable silicon content is obtained by performing hydrosilylation reaction after methoxy end capping. The invention adopts the conventional silicon-hydrogen addition reaction and the step-by-step polymerization reaction, and the provided synthesis steps are simple, easy to realize and high in yield; the composition of the traditional sealant is changed from the source, the obtained product has the characteristics of excellent bonding performance, weather resistance, durability and mechanical properties (higher tearing strength, breaking strength and modulus, moderate breaking elongation and hardness), and different application ranges can be realized by controlling the structure of polyether.

Description

Polyether with controlled silicon content and preparation method and application thereof
Technical Field
The invention relates to silicon modified polyether with controlled silicon content, a preparation method and application thereof
Background
The traditional polyurethane sealant does not conform to the environmental protection concept of China because the traditional polyurethane sealant contains free isocyanate, and bubbles are easily formed during curing, so that the application of the traditional polyurethane sealant in many fields is limited; the application of the silicone sealant is limited due to low tearing strength, poor coating property and easy pollution to building materials. The produced silane modified polyether sealant overcomes the defects of the two, has the advantages of the two, and is the main development direction of the current sealant.
At present, most of silane modified polyether sealants in the market are prepared by taking alkoxy-terminated polyether as a raw material, adding a certain proportion of reinforcing filler, plasticizer, water removing agent, tackifier and organic tin catalyst, and the obtained sealant has poor mechanical property, tensile strength and elasticity, poor aging property and incapability of maintaining longer service life due to the influence of crosslinking density.
Aiming at the defects that the elasticity and the strength of the existing silane modified polyether sealant cannot be well matched and the storage stability is poor, a plurality of patents and documents mention that the performance of the sealant is improved by changing the formula composition of the sealant.
CN106947423A discloses a silane modified polyether sealant composition, which is alkoxy terminated polyether with apparent viscosity of 7000 and 16000 mPa.s, one or more of bisaminosilane adhesion promoter, monoaminosilane adhesion promoter and alkoxy silane adhesion promoter is used as adhesion promoter, calcium carbonate, white carbon black, organic chelated tin catalyst, plasticizer and water removing agent. The performance of the sealant obtained by the formula is improved, but the problem of insufficient sealing performance still exists.
The alkoxy-terminated polyether is an alkoxy-terminated polyether with high tensile modulus, and has higher crosslinking density in the curing process, thereby being beneficial to improving the tensile strength. The specific mechanism is that the end group is a hydrolyzable siloxane group, and when a catalyst (amines, tin and the like) exists, the alkoxy in the end alkoxy is firstly hydrolyzed into a silanol group (Si-OH); followed by an Si-OH group or Si-OH and Si-OCH3The water or the methanol is released by condensation to form Si-O-Si bonds; finally, the silicon-oxygen-silicon (Si-O-Si) bonds are crosslinked into the elastomer with the body structure, wherein the Si-O-Si bonds are used as network crosslinking points, and flexible polyether chains are arranged between the crosslinking points.
In order to solve the above problems, a novel polyether sealant with controlled silicon content needs to be developed from the aspect of raw materials, so that a product with good adhesive property and excellent mechanical property and capable of meeting different requirements is obtained.
Disclosure of Invention
The invention aims to provide polyether with controllable silicon content, which has good bonding performance and excellent mechanical property and can meet different requirements, a preparation method thereof and application of the polyether as sealant.
According to the invention, polyether polyol containing double bonds and ether bonds is synthesized, methoxy group is adopted for end capping, and then hydrosilylation reaction is carried out on the polyether polyol to obtain polyether with controllable silicon content, and then conventional sealant is utilized to form the sealant which is excellent in bonding performance, weather resistance, durability and mechanical property.
According to a first aspect of the present invention, there is provided a silicon controlled content polyether having the formula:
Figure GDA0002664702620000021
wherein R is1As starter group, a C1-C10 hydrocarbon group (alkyl or alkenyl) or a C1-C10 hydroxyhydrocarbon group, preferably a C1-C6 alkyl group or a C1-C6 hydroxyalkyl group, n1 ═ 1 to 100, preferably 2 to 50, n2 ═ 1 to 100, preferably 2 to 50,
at least one of a 1-0, preferably 2-100, b 1-0, preferably 2-50, c 1-0, preferably 2-50, a1, b1, and c1 is greater than 0,
Figure GDA0002664702620000022
R3in order to be a repeating unit of the polymer,
Figure GDA0002664702620000023
wherein n3 is 1-100, n4 is 1-100;
SiX is a silane group, preferably one or more of dimethoxymethylhydrosilane, trimethoxyhydrosilane, or triethoxyhydrosilane.
According to the second aspect of the invention, the invention further provides a preparation method of the polyether with the controlled silicon content, which comprises the following steps
A. Preparing polyether polyol containing double bonds and ether bonds in a structural formula (1) by using monohydric alcohol or dihydric alcohol initiator, functional monomer and propylene oxide as raw materials;
Figure GDA0002664702620000024
wherein R is1As starter group, a C1-C10 hydrocarbon group or a C1-C10 hydroxyhydrocarbon group, preferably a C1-C6 alkyl group or a C1-C6 hydroxyalkyl group, n1 ═ 1 to 100, preferably 2 to 50, n2 ═ 1 to 100, preferably 2 to 50,
Figure GDA0002664702620000031
R3in order to be a repeating unit of the polymer,
Figure GDA0002664702620000032
wherein n3 is 1-100, n4 is 1-100,
R2as defined above;
B. carrying out methoxy end capping treatment on polyether polyol containing double bonds and ether bonds to obtain end capped polyether with a structural formula (2); the molecular weight of the compound in the structural formula 2 is preferably 5000-15000;
Figure GDA0002664702620000033
wherein R is1、R2、R3N1, n2 are as described above.
C. Taking the end-capped polyether as a raw material, and carrying out hydrosilylation reaction to obtain the polyether sealant with the controlled silicon content in the structural formula (3):
Figure GDA0002664702620000034
wherein R is1As starter group, a C1-C10 hydrocarbon group or a C1-C10 hydroxyhydrocarbon group, preferably a C1-C6 alkyl group or a C1-C6 hydroxyalkyl group, n1 ═ 1 to 100, preferably 2 to 50, n2 ═ 1 to 100, preferably 2 to 50,
at least one of a 1-0, preferably 2-100, b 1-0, preferably 2-50, c 1-0, preferably 2-50, a1, b1, and c1 is greater than 0,
Figure GDA0002664702620000035
R3in order to be a repeating unit of the polymer,
Figure GDA0002664702620000036
wherein n3 is 1-100, n4 is 1-100; SiX is a silane group, preferably one of dimethoxymethylhydrosilane, trimethoxyhydrosilane, or triethoxyhydrosilane.
In the invention, the molecular weight of the polyether with the double bond and the ether bond in the structural formula 1 obtained in the step A is 5000-15000. Wherein the mass fraction of the functional monomer in the total mass of the functional monomer and the propylene oxide is 5-10%, preferably 7-10%; the mass fraction of the propylene oxide in the total mass of the functional monomer and the propylene oxide is 80-95%, preferably 90-92%.
In the step A, the molar ratio of the initiator, the functional monomer and the propylene oxide is 1: 2-15: 70-150, preferably 1: 4-10: 78-123.
In the preparation of the polyether polyol, the reaction temperature of the step A is 100-125 ℃, the pressure reduction condition is-0.095-0.1 MPa, and the reaction time is 1-2 h.
In a preferred embodiment, the preparation of the polyether polyol described in step a comprises the steps of:
1) adding a catalyst into monohydric alcohol or dihydric alcohol initiator, replacing nitrogen (for example, three times), and then heating (for example, to 100-125 ℃) to dehydrate; 2) heating to the reaction temperature (for example, 110-150 ℃), and slowly adding the functional monomer and the propylene oxide or the mixture of the functional monomer and the propylene oxide into the system in the step 1); 3) curing until the pressure does not change any more; 4) the product is demonomerized to obtain the polyether with the target structural formula (1).
In the preparation of the polyether polyol, the catalyst in the step 1) is one of sodium, sodium hydroxide, potassium hydroxide, sodium methoxide and potassium methoxide, and the catalyst accounts for 0.05-0.2%, preferably 0.05-0.1% of the total mass of the reaction system (the total mass of the initiator, the functional monomer and the propylene oxide).
In the preparation of the polyether polyol, the initiator in the step 1) is one or more of monohydric alcohol and dihydric alcohol. Preferably, the initiator may be methanol 32 (nominal functionality 1), ethanol 46 (nominal functionality 1), ethylene glycol monomethyl ether 76 (nominal functionality 1), 1, 2-propylene glycol monomethyl ether 90 (nominal functionality 1), diethylene glycol monomethyl ether 120 (nominal functionality 1), ethylene glycol 62 (nominal functionality 2), 1, 2-propylene glycol/1, 3-propylene glycol 76 (nominal functionality 2), or neopentyl glycol 104 (nominal functionality 2).
In the preparation of the polyether polyol, the reaction temperature in the step 1) is 100-125 ℃, the pressure reduction condition is-0.095-0.1 MPa, and the reaction time is 1-2 h.
The polyether polyol is prepared, and the step 2) specifically comprises the following steps: heating to 110-150 ℃ after the reaction dehydration in the step 1), and adding a special functional monomer containing an epoxy group and an unsaturated double bond for polymerization.
Preferably, the functional monomer of step 2) may be one or more of 1, 2-epoxy-5-hexene, 1, 2-epoxy-9-decene and allyl glycidyl ether.
In the preparation of the polyether polyol, the mass fraction of the functional monomer in the step 2) in the total mass of the functional monomer and the propylene oxide is 5-10%, preferably 7-10%; the mass fraction of the propylene oxide in the total mass of the functional monomer and the propylene oxide is 80-95%, preferably 90-92%, and the adding mode of the monomer and the special monomer depends on the application performance, including but not limited to block copolymerization and random copolymerization polyether polyol.
In the preparation of the polyether polyol, the reaction time in the step 2) is 2-10 h, the reaction temperature is 110-150 ℃, and the reaction pressure is 0.1-0.4 MPa.
In the preparation of the polyether polyol, the curing time in the step 3) is 2-12 h, and the curing temperature is 110-150 ℃.
In the preparation of the polyether polyol, the demonomerization time in the step 4) is 1-2 h, and the temperature is maintained at 110-150 ℃.
In the present invention, the preparation of the polyether polyol described in step B comprises the following steps:
a) adding a catalyst into the polyether of the structural formula (1) and stirring for reaction;
b) vacuum degassing to remove low-boiling-point micromolecule substances;
c) cooling, and introducing methane chloride;
d) curing until the system pressure is not changed any more, removing the monomer and refining.
In the end capping treatment process, the catalyst in the step a) is an alkaline catalyst, preferably alkoxide such as sodium methoxide, potassium hydroxide and sodium hydroxide, the catalyst accounts for 0.05-0.2%, preferably about 0.1% of the total mass of the polyether polyol and the monochloromethane, the reaction temperature is 95-105 ℃, and the reaction time is 1-2 hours. In the end capping treatment process, the temperature in the step b) is 95-105 ℃, and the degassing time is 1 h; the temperature in step c) is 70-90 ℃, preferably about 80 ℃ and the reaction time is 1 h.
The molar mass ratio of the introduced amount of the methane chloride to the polyether polyol of the formula (1) in the step c) is 1-3, and if the formula (1) is a monoalcohol, the molar mass ratio is 1: 1-2, preferably 1: 1.1-1.6; if the formula (1) is a dihydric alcohol, the molar mass ratio is 1:2 to 3, preferably 1:2.2 to 2.8.
The curing temperature in the step d) is 90-100 ℃, and the curing time is 2-5 h.
Preferably, the refining treatment comprises neutralization with a neutralizing agent, adsorption with an adsorbent, and filtration with a filter aid.
In the end-capping treatment process, the demonomerization temperature in the step d) is 110-120 ℃, and the demonomerization time is 1-2 h; the neutralizing agent for the refining treatment is an aqueous phosphoric acid solution, for example, a 50-90 wt%, preferably about 85% aqueous phosphoric acid solution, and the molar ratio of the phosphoric acid solution to the catalyst in the step a) is 0.7-1.2, preferably 0.8-1.0, and accounts for 0.05-0.3 wt%, preferably about 0.1 wt% of the polyether polyol; the adsorbent is magnesium silicate, and the mass fraction of the adsorbent is 1-5% of polyether; the filter aid is diatomite and has a mass fraction of 0.2-1.0 wt%, preferably about 0.5% of the mass of the polyether.
In the present invention, the preparation of the polyether polyol described in step C comprises the steps of:
dehydrating; adding isopropanol solution of chloroplatinic acid into the system, and adding silane under a stirring state; thirdly, removing unreacted silane after the system reaction is finished.
In the hydrosilylation reaction, the dehydration temperature in the first step is 85-95 ℃, and the treatment time is 1-2 hours.
In the hydrosilylation reaction, the silane reagent adopted in the step II is preferably one or more of dimethoxymethylhydrosilane, trimethoxyhydrosilane or triethoxyhydrosilane, the molar ratio of silane to terminated polyether is determined according to the functionality of terminated polyether, and if the terminated polyether is a single function, the molar ratio of the terminated polyether to the terminated polyether is 1: 1-2, preferably 1: 1.2-1.6; if the blocked polyether is difunctional, the molar mass ratio is from 1:2 to 3, preferably from 1:2.2 to 2.8.
The reaction temperature is kept at 85-95 ℃; the catalyst chloroplatinic acid is a 1-10 wt.%, preferably about 5% isopropanol solution, with the catalyst being used in an amount of 10-100ppm (calculated as polyether mass) based on platinum.
In the hydrosilylation reaction, the demonomerization temperature is kept at 85-95 ℃ and the reaction time is 3-5 h.
The invention further relates to the use of the above silicon controlled content polyether as a sealant.
The invention has the advantages that:
according to the invention, polyether polyol containing double bonds and ether bonds is synthesized, methoxy group is adopted for end capping, and then hydrosilylation reaction is carried out on the polyether polyol to obtain polyether with controllable silicon content, and then conventional sealant is utilized to form the sealant which is excellent in bonding performance, weather resistance, durability and mechanical property. The obtained sealant has good bonding property and excellent mechanical property, and can meet different requirements.
Detailed Description
The present invention will be further described with reference to the following examples.
The test method involved in the embodiment comprises a hydroxyl value test, an acid value test, a water content determination and an unsaturation degree test, wherein the hydroxyl value test is carried out by referring to GB/T12008.3-2009 plastic polyether polyol part 3: determination of the hydroxyl value; acid value test the test was carried out with reference to GB/T12008.5-2010 Plastic polyether polyol part 5 acid value determination; the unsaturation degree is tested according to GB/T12008.6-2010 plastic polyether polyol part 6: the measurement of the unsaturation degree; water content testing the test was carried out with reference to the determination of the water content of the polyols used in polyurethane production from GB/T22313-2008 plastic.
Example 1
The molecular weight of the structure (1) designed in this example is 5000, wherein a PO unit (78.9mol) accounts for 92.1% of the total monomer mass, a special monomer adopts 1, 2-epoxy-5-hexene (4mol) which accounts for 7.90% of the total monomer mass, the theoretical hydroxyl value is 11.2mgKOH/g, and the theoretical unsaturation degree is 0.8 mmol/g; the theoretical blocking rate of the blocking is 100 percent by adopting methoxy blocking; the hydrosilylation unsaturation degree is theoretically 0 mmol/g. The silane adopts dimethoxymethylhydrosilane.
Adding 3.2g of methanol as an initiator into a 1L kettle, adding 0.5g (0.1%) of sodium methoxide serving as a catalyst, replacing with nitrogen, reducing the pressure to-0.1 MPa, heating to 100 ℃, and removing water generated in the reaction for 1.5 hours; raising the temperature to 110 ℃, calculating the mass of the needed propylene oxide monomer to be 457.5g and the mass of the needed 1, 2-epoxy-5-hexene functional monomer to be 39.26g, mixing the two monomers, slowly adding the mixture into a kettle, keeping the reaction pressure not to exceed 0.4MPa, and keeping the total reaction time to be 4 h; after the feeding is finished, the mixture is cured until the reaction pressure is not changed any more, and the total curing time is 3 h.
Adding 6.48g of sodium methoxide (21.6 g of 30% methanol solution) according to the molar ratio of 1:1.2, stirring and reacting for 1h, keeping the temperature at 100 ℃, and degassing for 1 h; slowly introducing 7.58g of methane chloride (polyether: methane chloride is 1:1.5) for 1 h; after the feeding is finished, curing is carried out until the reaction pressure does not change any more, and the total curing time is 3 hours; carrying out vacuum removal treatment for 1 h; and (3) neutralizing, adding 85 mass percent phosphoric acid aqueous solution accounting for 0.12 percent of the total mass of the crude polyether, 5 mass percent water and 5 mass percent adsorbent magnesium silicate for refining, adding filter aid diatomite accounting for 0.5 percent of the total mass of the crude polyether, and filtering to obtain the target polyether, wherein the water content and the acid value of the product are qualified (the water content is less than 0.05 percent, the acid value is less than 0.1mgKOH/g, the same below).
300g of the purified polyether was taken, the temperature was maintained at 90 ℃, 1.596g of a 5% isopropyl alcohol solution of chloroplatinic acid (5% isopropyl alcohol solution of chloroplatinic acid required in terms of 100ppm Pt) was added to the system, 25.48g of dimethoxymethylhydrosilane was added under stirring to react for 4 hours, and then the monomer was removed under vacuum.
The above product measured a hydroxyl value of 12mgKOH/g (theoretical hydroxyl value of 11.2mgKOH/g), which confirmed that the molecular weight of formula 1 had reached the calculated molecular weight of 4675, and the measured unsaturation was 0.75mmol/g (theoretical unsaturation of 0.8 mmol/g). The end capping rate of the methoxy end capping in the structural formula 2 is 95 percent; the degree of hydrosilylation unsaturation was 0.05mmol/g
Example 2
This example designs a molecular weight 8000 for structure (1) where PO units (123.33mol) account for 90.12% of the total monomer mass, 1, 2-epoxy-5-hexene (8mol) as the specialty monomer accounts for 9.89% of the total monomer mass, the theoretical hydroxyl number is 14.03mgKOH/g, and the theoretical unsaturation is 1 mmol/g. The theoretical hydroxyl value of the end capping by using the methoxyl is 0mgKOH/g, and the theoretical unsaturation degree of the hydrosilylation is 0 mmol/g. The silane adopts dimethoxymethylhydrosilane.
Adding 6.2g of ethylene glycol as an initiator into a 1L kettle, adding 0.8g (0.1%) of sodium methoxide serving as a catalyst, replacing with nitrogen, reducing the pressure to-0.1 MPa, heating to 100 ℃, and removing water generated in the reaction for 1.5 hours; raising the temperature to 110 ℃, calculating the mass of the required propylene oxide monomer to be 715.2g and the mass of the required 1, 2-epoxy-5-hexene functional monomer to be 78.5g, mixing the two monomers, slowly adding the mixture into a kettle, keeping the reaction pressure not to exceed 0.4MPa, and keeping the total reaction time to be 4 h; after the feeding is finished, the mixture is cured until the reaction pressure is not changed any more, and the total curing time is 3 h.
Adding 11.88g of sodium methoxide, namely 39.6g of 30% methanol solution according to the molar ratio of 1:2.2, stirring and reacting for 1h, keeping the temperature at 100 ℃, and degassing for 1 h; slowly introducing 12.63g of methane chloride (polyether: methane chloride is 1:2.5) for 1 h; after the feeding is finished, curing is carried out until the reaction pressure does not change any more, and the total curing time is 3 hours; carrying out vacuum removal treatment for 1 h; and (3) neutralizing, adding 85 mass percent phosphoric acid aqueous solution accounting for 0.24 percent of the total mass of the crude polyether, 5 mass percent water and 5 mass percent adsorbent magnesium silicate for refining, adding filter aid diatomite accounting for 0.5 percent of the total mass of the crude polyether, and filtering to obtain the target polyether, wherein the water content and the acid value of the product are qualified (the water content is less than 0.05 percent, the acid value is less than 0.1mgKOH/g, the same below).
500g of the purified polyether was taken, the temperature was maintained at 90 ℃, 2.66g of a 5% isopropyl alcohol solution of chloroplatinic acid (5% isopropyl alcohol solution of chloroplatinic acid required in terms of 100ppm Pt) was added to the system, 53.1g of dimethoxymethylhydrosilane was added under stirring for 4 hours, and the monomer was removed under vacuum.
The hydroxyl value of the product structure 1 is measured to be 15mgKOH/g (the theoretical hydroxyl value is 14.03mgKOH/g), the molecular weight of the structural formula 1 is proved to reach the calculated molecular weight 7480, and the measured unsaturation degree is 0.96mmol/g (the theoretical unsaturation degree is 1 mmol/g). The end capping rate of the methoxy end capping in the structural formula 2 is 93 percent; the hydrosilylation unsaturation degree was 0.08 mmol/g.
Example 3
This example designs a molecular weight of 10000 for structure (1), where PO units (78.9mol) account for 90.77% of the total monomer mass, allyl glycidyl ether (8mol) accounts for 9.23% of the total monomer mass, the theoretical hydroxyl number is 11.22mgKOH/g, and the theoretical unsaturation is 0.8 mmol/g. The theoretical hydroxyl value of the end capping by using the methoxyl is 0mgKOH/g, and the theoretical unsaturation degree of the hydrosilylation is 0 mmol/g. The silane adopts trimethoxy hydrosilane.
Adding 10.4g of neopentyl glycol serving as an initiator into a 1L kettle, adding 1g (0.1%) of sodium methoxide serving as a catalyst, replacing with nitrogen, reducing the pressure to-0.1 MPa, and heating to 100 ℃ to remove water generated in the reaction for 1.5 h; raising the temperature to 110 ℃, calculating the mass of the required propylene oxide monomer to be 898.26g and the mass of the required allyl glycidyl ether functional monomer to be 91.36g, mixing the two monomers, slowly adding the mixture into a kettle, keeping the reaction pressure not more than 0.4MPa, and keeping the total reaction time to be 4 h; after the feeding is finished, the mixture is cured until the reaction pressure is not changed any more, and the total curing time is 3 h.
Adding 11.88g of sodium methoxide, namely 39.6g of 30% methanol solution according to the molar ratio of 1:2.2, stirring and reacting for 1h, keeping the temperature at 100 ℃, and degassing for 1 h; slowly introducing 12.63g of methane chloride (polyether: methane chloride is 1:2.5) for 1 h; after the feeding is finished, curing is carried out until the reaction pressure does not change any more, and the total curing time is 3 hours; carrying out vacuum removal treatment for 1 h; and (3) neutralizing, adding 85 mass percent phosphoric acid aqueous solution accounting for 0.24 percent of the total mass of the crude polyether, 5 mass percent water and 5 mass percent adsorbent magnesium silicate for refining, adding filter aid diatomite accounting for 0.5 percent of the total mass of the crude polyether, and filtering to obtain the target polyether, wherein the water content and the acid value of the product are qualified (the water content is less than 0.05 percent, the acid value is less than 0.1mgKOH/g, the same below).
500g of the purified polyether was taken, the temperature was maintained at 90 ℃, 4.26g of a 5% isopropyl alcohol solution of chloroplatinic acid (5% isopropyl alcohol solution of chloroplatinic acid required in terms of 100ppm Pt) was added to the system, 48.8 g of dimethoxymethylhydrosilane was added under stirring for 4 hours, and the monomer was removed under vacuum.
The hydroxyl value of the product structure 1 is measured to be 12mgKOH/g (the theoretical hydroxyl value is 11.22mgKOH/g), the molecular weight of the structural formula 1 is proved to reach the calculated molecular weight of 9350, and the measured unsaturation degree is 0.77mmol/g (the theoretical unsaturation degree is 0.8 mmol/g). The end capping rate of the methoxy end capping in the structural formula 2 is 90 percent; the hydrosilylation unsaturation degree was 0.06 mmol/g.
Example 4
This example designs the molecular weight of structure (1) at 15000, where PO units (78.9mol) account for 91.69% of the total monomer mass, allyl glycidyl ether (10mol) accounts for 7.67% of the total monomer mass, the theoretical hydroxyl number is 7.48mgKOH/g, and the theoretical unsaturation is 0.67 mmol/g. The theoretical hydroxyl value of the end capping by using the methoxyl is 0mgKOH/g, and the theoretical unsaturation degree of the hydrosilylation is 0 mmol/g. The silane adopts trimethoxy hydrosilane.
Adding 10.4g of neopentyl glycol serving as an initiator into a 2L kettle, adding 1.5g (0.1%) of sodium methoxide serving as a catalyst, replacing with nitrogen, reducing the pressure to-0.1 MPa, and heating to 100 ℃ to remove water generated in the reaction for 1.5 hours; raising the temperature to 110 ℃, calculating the mass of the required propylene oxide monomer to be 1365.8g and the mass of the required allyl glycidyl ether functional monomer to be 114.25g, mixing the two, slowly adding the two into the kettle, keeping the reaction pressure not more than 0.4MPa, and keeping the total reaction time to be 4 h; after the feeding is finished, the mixture is cured until the reaction pressure is not changed any more, and the total curing time is 3 h.
Adding 11.88g of sodium methoxide, namely 39.6g of 30% methanol solution according to the molar ratio of 1:2.2, stirring and reacting for 1h, keeping the temperature at 100 ℃, and degassing for 1 h; slowly introducing 12.63g of methane chloride (polyether: methane chloride is 1:2.5) for 1 h; after the feeding is finished, curing is carried out until the reaction pressure does not change any more, and the total curing time is 3 hours; carrying out vacuum removal treatment for 1 h; and (3) neutralizing, adding 85 mass percent phosphoric acid aqueous solution accounting for 0.24 percent of the total mass of the crude polyether, 5 mass percent water and 5 mass percent adsorbent magnesium silicate for refining, adding filter aid diatomite accounting for 0.5 percent of the total mass of the crude polyether, and filtering to obtain the target polyether, wherein the water content and the acid value of the product are qualified (the water content is less than 0.05 percent, the acid value is less than 0.1mgKOH/g, the same below).
500g of the purified polyether was taken, the temperature was maintained at 90 ℃, 5.33g of a 5% isopropyl alcohol solution of chloroplatinic acid (5% isopropyl alcohol solution of chloroplatinic acid required in terms of 100ppm Pt) was added to the system, 61g of dimethoxymethylhydrosilane was added under stirring for 4 hours, and the monomer was removed under vacuum.
The hydroxyl value of the product structure 1 is measured to be 8mgKOH/g (the theoretical hydroxyl value is 7.48mgKOH/g), the molecular weight of the structural formula 1 is proved to reach the calculated molecular weight of 14025, and the measured unsaturation degree is 0.61mmol/g (the theoretical unsaturation degree is 0.67 mmol/g). The end capping rate of the methoxy end capping in the structural formula 2 is 89 percent; the hydrosilylation unsaturation degree was 0.05 mmol/g.
Comparative example 1
The preparation of the polyether of the comparative example comprises five steps:
ethylene glycol is adopted as an initiator, 6.2g of ethylene glycol is added into a 1L kettle to be used as the initiator, 0.8g (0.1%) of sodium methoxide serving as a catalyst is added, nitrogen is replaced, the pressure is reduced to-0.1 MPa, and the temperature is raised to 100 ℃ to remove water generated in the reaction for 1.5 h; raising the temperature to 110 ℃, calculating the mass of the required propylene oxide monomer to be 793.8g, slowly adding the propylene oxide monomer into the kettle, keeping the reaction pressure not to exceed 0.4MPa, and keeping the total reaction time to be 5 h; after the feeding is finished, the mixture is aged until the reaction pressure is not changed any more, and the total aging time is 6 h.
Taking the alcohol esterified polyether obtained in the last step, adding 26.4g of allyl bromide with the molar ratio of 1:2.2, introducing nitrogen for protection, stirring and mixing uniformly, heating to 110 ℃, and keeping the temperature for reaction. After completion, the excess allylating reagent was removed under reduced pressure and the crude product was refined.
And (2) neutralizing, adding 1.92g of phosphoric acid aqueous solution with the mass fraction of 85%, 40g of 5% water and 40g of adsorbent magnesium silicate with the mass fraction of 5%, which are 0.24% of the total mass of the crude polyether, for refining, adding 4g of diatomite which is 0.5% of the total mass of the crude polyether, and filtering to obtain the target polyether, wherein the water content and the acid value of the product are qualified (the water content is less than 0.05%, and the acid value is less than 0.1 mgKOH/g).
500g of the purified polyether was taken, the temperature was maintained at 90 ℃, 2.66g of a 5% isopropyl alcohol solution of chloroplatinic acid (5% isopropyl alcohol solution of chloroplatinic acid required in terms of 100ppm Pt) was added to the system, 53.1g of dimethoxymethylhydrosilane was added under stirring for 4 hours, and the monomer was removed under vacuum.
Slowly introducing 12.63g of methane chloride (polyether: methane chloride is 1:2.5) for 1 h; after the feeding is finished, curing is carried out until the reaction pressure does not change any more, and the total curing time is 3 hours; and (4) carrying out vacuum removal treatment for 1h to obtain the target polyether.
The measured hydroxyl value of the product is 16mgKOH/g (the theoretical hydroxyl value is 14.03mgKOH/g), and the molecular weight of the target product is proved to reach the calculated molecular weight of 7012.
Example 6
This embodiment is an application embodiment
The obtained silicon modified polyether is prepared into the sealant by adopting the following formula:
Figure GDA0002664702620000111
Figure GDA0002664702620000112
by comparing the main performance of the sealant and the bonding force, the sealant obtained by adopting 1, 2-epoxy-5-hexene (8mol) as a special monomer in example 2 with the molecular weight of 8000g/mol has the best performance, the bonding force is 95.8Pa, which is much higher than that of the sealant obtained by adopting the molecular weight of 7000g/mol and siloxane end capping (2mol) in the comparative example, and the bonding force is 79.6 Pa. The main reason is that the siloxane content of the sealant in example 2 is high, the number of crosslinking points is increased, and the adhesion ability is limited by the molecular weight, generally, the elongation is increased and the tensile strength is decreased with the increase of the relative molecular weight, and when the molecular weight is larger and the number of crosslinking points is more, the viscosity of the sealant itself is larger, so that the adhesion force is decreased. Therefore, in four groups of embodiments, the sealant of embodiment 2, which has a molecular weight of 8000g/mol and adopts 1, 2-epoxy-5-hexene (8mol) as a special monomer, has the best sealing performance, and can be used for products with high requirements on adhesive force, such as surface pasting of wood, steel, stone, concrete and the like.

Claims (19)

1. Polyether with controlled silicon content has the following structural formula:
Figure FDA0002719847020000011
wherein R is1Is an initiator group selected from C1-C10 alkyl or C1-C10 hydroxy alkyl, n 1-1-100, n 2-1-100,
0-100 for a1, 0-100 for b1, 0-100 for c1, more than 0 for at least one of a1, b1, and c1,
R3in order to be a repeating unit of the polymer,
Figure FDA0002719847020000012
wherein n3 is 1-100, n4 is 1-100,
Figure FDA0002719847020000013
SiX is a silane group.
2. The scr-containing polyether of claim 1, wherein n1 is 2-50 and n2 is 2-50.
3. The scr-containing polyether of claim 1 or 2, wherein a 1-2-50, b 1-2-50, and c 1-2-50.
4. The controlled silicon content polyether of claim 1, wherein SiX is one or more of a dimethoxymethylhydrosilane group, a trimethoxyhydrosilane group, and a triethoxyhydrosilane group.
5. The method of claim 1, wherein the step of preparing the controlled silicon content polyether comprises the steps of:
A. preparing polyether polyol containing double bonds and ether bonds in a structural formula (1) by using monohydric alcohol or dihydric alcohol initiator, functional monomer and propylene oxide as raw materials;
Figure FDA0002719847020000014
wherein R is1As starter group, at least one of the groups C1-C10 hydrocarbon or C1-C10 hydroxyhydrocarbon, n 1-1-100, n 2-1-100, x-a 1+ b1+ C1, a 1-0-100, b 1-0-100, C1-0-100, a1, b1, and C1 is greater than 0,
Figure FDA0002719847020000021
R3in order to be a repeating unit of the polymer,
Figure FDA0002719847020000022
wherein n 3-1-100, n 4-1-100, R2As defined above;
B. carrying out methoxy end capping treatment on polyether polyol containing double bonds and ether bonds to obtain end capped polyether with a structural formula (2);
Figure FDA0002719847020000023
wherein R is1、R2、R3N1, n2 are as defined above;
C. carrying out hydrosilylation reaction by using terminated polyether as a raw material to obtain polyether with controlled silicon content in a structural formula (3):
Figure FDA0002719847020000024
wherein R is1Is an initiator group selected from C1-C10 alkyl or C1-C10 hydroxy alkyl, n 1-1-100, n 2-1-100,
0-100 for a1, 0-100 for b1, 0-100 for c1, more than 0 for at least one of a1, b1, and c1,
R3in order to be a repeating unit of the polymer,
Figure FDA0002719847020000025
wherein
n3＝1-100，n4＝1-100；
Figure FDA0002719847020000026
SiX is a silane group.
6. The production method according to claim 5, wherein the monohydric or dihydric alcohol is selected from one or more of methanol, ethanol, ethylene glycol monomethyl ether, 1, 2-propylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, neopentyl glycol;
the functional monomer is selected from one or more of 1, 2-epoxy-5-hexene, 1, 2-epoxy-9-decene and allyl glycidyl ether.
7. The preparation method according to claim 6, wherein in the step A, the molar ratio of the initiator to the functional monomer to the propylene oxide is 1: 2-15: 70-150.
8. The method according to claim 7, wherein the molar ratio of the initiator to the functional monomer to the propylene oxide is 1:4 to 10:78 to 123.
9. The process according to claim 5, wherein the number average molecular weight of the compound of formula (2) is 5000 to 15000.
10. The production method according to claim 5 or 6, wherein the polyether polyol production in step A comprises the steps of:
1) using monohydric alcohol or dihydric alcohol initiator as initiator, adding catalyst, replacing with nitrogen, heating and dehydrating; 2) heating to reaction temperature, and slowly adding a functional monomer and propylene oxide or a mixture of the functional monomer and the propylene oxide into the system in the step 1); 3) curing until the pressure is not changed; 4) and (3) obtaining the polyether with the target structural formula (1) after the product is subjected to demonomerization.
11. The preparation method according to claim 10, wherein the catalyst in step 1) is one of sodium, sodium hydroxide, potassium hydroxide, sodium methoxide and potassium methoxide, and the mass of the catalyst is 0.05-0.2% of the total mass of the reaction system, i.e. the total mass of the initiator, the functional monomer and the propylene oxide;
the temperature of the step 1) is 100-125 ℃, the pressure reduction condition is-0.095-0.1 MPa, and the reaction time is 1-2 h;
the step 2) comprises the following steps: heating to 110-150 ℃ after the reaction dehydration in the step 1) is finished, and adding a functional monomer containing an epoxy group and an unsaturated double bond for polymerization reaction;
the reaction time of the step 2) is 2-10 h, the reaction temperature is 110-150 ℃, and the reaction pressure is 0.1-0.4 MPa;
the curing time in the step 3) is 2-12 hours, and the curing temperature is 110-150 ℃;
the demonomerization time in the step 4) is 1-2 h, and the temperature is maintained at 110-150 ℃.
12. The preparation method according to claim 11, wherein the mass of the catalyst is 0.05 to 0.1% of the total mass of the reaction system, that is, the total mass of the initiator, the functional monomer and the propylene oxide.
13. The method according to claim 5, wherein the preparation of polyether polyol in step B comprises the steps of:
a) adding a catalyst into the polyether of the structural formula (1) and stirring for reaction;
b) vacuum degassing to remove low-boiling-point micromolecule substances;
c) cooling, and introducing methane chloride;
d) curing until the system pressure is not changed any more, removing the monomer and refining.
14. The preparation method of claim 13, wherein the catalyst in step a) is a basic catalyst, the mass of the catalyst accounts for 0.05-0.2% of the total mass of the polyether polyol and the methyl chloride, the reaction temperature is 95-105 ℃, and the reaction time is 1-2 h;
the temperature in the step b) is 95-105 ℃, and the degassing time is 1 h;
the temperature in the step c) is 70-90 ℃, and the reaction time is 1 h;
the molar mass ratio of the introduced amount of the methane chloride to the polyether polyol in the formula (1) in the step c) is 1-3, and if the formula (1) is a monohydric alcohol, the molar mass ratio is 1: 1-2; if the formula (1) is dihydric alcohol, the molar mass ratio is 1: 2-3;
curing temperature in the step d) is 90-100 ℃, and curing time is 2-5 h;
the refining treatment in step d) comprises neutralization with a neutralizing agent, adsorption with an adsorbent, and filtration with a filter aid;
the demonomerization temperature in the step d) is 110-120 ℃, and the demonomerization time is 1-2 h; the neutralizing agent for refining treatment is phosphoric acid aqueous solution, and the molar ratio of the phosphoric acid aqueous solution to the catalyst in the step a) is 1: 0.7-1.2, accounting for 0.05-0.3 wt% of the polyether polyol; the adsorbent is magnesium silicate, and the mass fraction of the adsorbent is 1-5% of polyether; the filter aid is diatomite, and the mass fraction of the filter aid is 0.2-1.0 wt% of the mass of the polyether.
15. The production method according to claim 14, wherein the basic catalyst is sodium methoxide, potassium hydroxide, sodium hydroxide; the molar mass ratio of the introduced amount of the methane chloride to the polyether polyol in the formula (1) in the step c) is 1-3, and if the formula (1) is a monohydric alcohol, the molar mass ratio is 1: 1.1-1.6; when the formula (1) is a diol, the molar mass ratio is 1: 2.2-2.8.
16. The process according to claim 14, wherein the neutralizing agent for the purification treatment is an aqueous phosphoric acid solution, and the molar ratio of the neutralizing agent to the catalyst in the step a) is 1:0.8 to 1.0.
17. The method of claim 5, wherein the hydrosilylation in step C comprises the steps of:
dehydrating; adding isopropanol solution of chloroplatinic acid into the system, and adding silane under a stirring state; thirdly, removing unreacted silane after the system reaction is finished.
18. The preparation method according to claim 17, wherein in the hydrosilylation reaction, the dehydration temperature in the step (i) is 85 to 95 ℃, and the treatment time is 1 to 2 hours; and/or
The silane reagent adopted in the addition reaction in the second step is one or more of dimethoxymethylhydrosilane, trimethoxyhydrosilane and triethoxyhydrosilane; the reaction temperature is kept at 85-95 ℃; the catalyst chloroplatinic acid is 1-10 wt% of isopropanol solution, wherein the dosage of the catalyst is 10-100ppm calculated by platinum and calculated by the total mass of polyether; and/or
And the demonomerization temperature is kept at 85-95 ℃, and the reaction time is 3-5 h.
19. Use of a thyristor-containing polyether according to any one of claims 1 to 4 or a thyristor-containing polyether obtained by the preparation process according to any one of claims 5 to 18 as a sealant.
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