CN113461902B

CN113461902B - Siloxane-terminated polymer homo-polymerization preparation method and moisture-curing composition

Info

Publication number: CN113461902B
Application number: CN202010236302.4A
Authority: CN
Inventors: 娄从江
Original assignee: Individual
Current assignee: Individual
Priority date: 2020-03-30
Filing date: 2020-03-30
Publication date: 2023-03-14
Anticipated expiration: 2040-03-30
Also published as: CN113461902A

Abstract

A homo-polymerization process for preparing a siloxane-terminated polymer (P) having a high end-capping rate and a high reactivity, and a moisture-curable composition (C) comprising the polymer are disclosed. By the preparation method, the siloxane end-capped polymer (P) can be prepared without containing tin catalysts, so that the product has the excellent characteristics of high end capping rate, insensitivity to moisture in air and the like, and the polymer (P) has good storage stability. The moisture-curable composition (C) should further contain, based on 100 parts by mass of the polymer (P): from 0.1 to 35 parts of a combination of a catalyst (C1) selected from the group consisting of metal-containing catalysts, guanidines and imidazoles and a co-catalyst (C2) comprising units of the formula (II), which moisture-curing composition (C) has a very high moisture-curing activity, dries quickly and is capable of complete detackification, and which composition (C) is particularly suitable for use in adhesives, sealants, coatings and the like.

Description

Siloxane-terminated polymer homo-polymerization preparation method and moisture-curing composition

Technical Field

The invention relates to a siloxane end-capped polymer preparation method and a moisture-curing composition, in particular to a siloxane end-capped polymer homotype polymerization reaction preparation method; and the preparation and application of a moisture-curing composition containing the siloxane-terminated polymer, belonging to the technical field of materials.

Background

Modification of oligomer and polymer functionalization by polymer-analogous reactions is an important synthetic method in the chemical industry, which can adjust and modify polymer properties such as reactivity, crosslinking, adhesion, solubility, morphology and thermal stability of the polymer. The reaction conditions of the polymer with the same type are the same or similar, continuous production can be realized through the design of a production line, the stability and the uniformity of the product are beneficial, and the production efficiency can be greatly improved.

The sealing adhesive based on the polymer system blocked or modified by alkoxy silane is invented by Japanese Brillouin chemistry for the first time in 1979, and becomes a very important variety after silicone and polyurethane elastic sealing adhesive after decades of development, the sealing adhesive is vigorously developed in the building field, particularly rapidly increased in nearly 10 years, and the sealing adhesive is widely applied in the widening fields of waterproof coatings, industrial assembly, electronic packaging and protection and the like. When the polymer with siloxane groups contacts water or moisture in air, the siloxane groups with high reactivity are hydrolyzed, crosslinked and condensed, and release small molecular alcohols, and finally the elastomer with Si-O-Si as bonding is formed. Such systems are particularly suitable for use in sealants, adhesives and coatings.

The main current siloxane-terminated polymers are siloxane-terminated polyether and siloxane-terminated polyurethane, and the synthetic routes mainly comprise the following steps:

(1) And (3) carrying out hydrosilylation reaction on the alkenyl-terminated polyether or polyurethane and hydrogen siloxane. Specific information can be found in japanese patent: showa 53-134095.

(2) High molecular weight polyoxypropylene ether polyols or hydroxyl terminated prepolymers made from excess polyoxypropylene ether polyols and insufficient amounts of polyisocyanates are reacted with isocyanatosiloxanes to attach the siloxanes to the ends of the polyether or polyurethane via urethane linkages. For specific information, see patents: EP0931800, EP0070475 and US5068304.

(3) Polyoxypropylene polyols are reacted with excess polyisocyanate to form isocyanate terminated polyurethane prepolymers, which are reacted with aminoalkoxysilanes, particularly secondary aminoalkoxysilanes, to attach the siloxane to the ends of the polyurethane via urea linkages. For specific information, see patents: EP059360, EP0082528, EP1256595.

There are currently commercial siloxane-terminated polymers available in all three routes, and the resulting products are used primarily for the production of sealants and adhesives.

However, each of the above three routes has its own limitations.

The process of the route (1) is complex, more inactive polymers are generated by side reaction, the obtained siloxane end-capped polymer has lower end-capping rate and poorer activity, the surface of the prepared sealant product is difficult to be tack-free, and a large amount of special chelated tin catalysts are needed to realize room-temperature moisture curing. In addition, hydrogen-containing siloxane is needed in the preparation process of the polymer, hydrogen is easy to generate, and the risk of explosion is caused.

The high molecular weight polyoxypropylene ether polyol used for direct end capping in the route (2) needs more than 10000g/mol of molecular weight to have good elasticity, so that the high molecular weight polyether has relatively few suppliers, higher price and relatively poor product stability; in addition, the high molecular weight polyoxypropylene ether polyol or hydroxyl-terminated prepolymer prepared from excessive polyoxypropylene ether polyol and insufficient polyisocyanate is secondary hydroxyl end, the hydroxyl content is low, the reaction activity with isocyanate siloxane is low, high-activity urethane generation catalysts such as organic tin and amine need to be added, and the catalysts are also catalysts for promoting siloxane hydrolysis and crosslinking, so that the storage stability of the prepared siloxane-terminated polyurethane is greatly influenced.

The reaction speed of the end-capping agent amino siloxane in the route (3) and the isocyanate end-capped polyurethane prepolymer is high and violent, the polyurethane prepolymer is easy to implode, the viscosity is sharply increased, and the polyurethane prepolymer is caked. The compatibility between the urea bond with strong polarity and strong crystallinity and the polyether main chain is poor, so that the prepared siloxane end-capped polymer has very high viscosity, and the subsequent use process is inconvenient. In addition, if the aminosiloxane is basic, it remains, the storage stability of the resulting siloxane-terminated polymer will be greatly affected.

In addition to the urethane-forming reactions expected to occur in polymer preparation, other side reactions may also occur when endcapping with the isocyanatosiloxanes, leading to degradation and loss of the endcapping agent, the isocyanatosiloxane. Particularly, siloxane groups are hydrolyzed in the polymerization process to generate micromolecular alcohol, the micromolecular alcohol has reaction activity far higher than that of hydroxyl in a hydroxyl end-capping prepolymer, the micromolecular alcohol reacts with isocyanate of an end-capping reagent to generate carbamate, and particularly, under the existence of a catalyst containing metallic tin or amine carbamate, siloxane is greatly promoted to be hydrolyzed when meeting water, so that the end-capping reagent is ineffective, and the low-functionalization effect of a polymer is generated.

In view of the above, it is desirable to develop and design a new synthesis method and process to improve the blocking efficiency and reduce the side reactions of blocking, so that the siloxane-terminated polymer can be synthesized without adding a urethane-forming reaction catalyst with high activity for promoting the hydrolysis of alkoxysilane, and the prepared siloxane-terminated polymer has high blocking rate, low moisture sensitivity and excellent storage stability.

Disclosure of Invention

In order to solve the defects of the prior art, one of the purposes of the invention is to provide a homo-type polymerization reaction preparation method of siloxane end-capped polymer (P), which is a homo-type polymer preparation method of adding one clearing step into three synthesis steps, wherein the obtained product has high end-capping rate, is not sensitive to moisture in air, and has good storage stability.

It is a further object of the present invention to provide a moisture-curing composition (C) which is very highly moisture-curing, dries quickly and is completely tack-free, and is particularly suitable for adhesives, sealants and coatings and the like.

In order to achieve the above object, the present invention adopts the following technical solutions:

the invention firstly discloses a homotype polymerization preparation method of siloxane end-capped polymer (P), which comprises three homotype polymerization reaction steps and one elimination reaction step for continuous preparation;

the siloxane-terminated polymer (P) has the structure of formula (I):

P ¹ [-CH ₂ -O-C(＝O)-NH-A-Si(O-R ¹ ) _a R ² _(3-a) ] _b (I)

in formula (I):

P ¹ independently represents a polymer backbone moiety having a number average molecular weight of from 500 to 30000 g/mol; is a b-valent polymeric backbone moiety linked via a carbon, nitrogen, oxygen or sulfur atom, preferably a polyoxypropylene ether moiety or segment or a polyurethane moiety or segment prepared from a polyoxypropylene ether, more preferably a polyurethane moiety or segment prepared from a polyoxypropylene ether;

R ¹ identical or different at each occurrence and represents a monovalent hydrocarbon radical of 1 to 4 carbon atoms, preferably a methyl (-CH 3) or ethyl (-CH 2CH 3);

R ² identical or different at each occurrence and represents a monovalent hydrocarbon radical of 1 to 20 carbon atoms, preferably methyl;

a, which is identical or different at each occurrence, represents a divalent hydrocarbon radical of a chain of 1 to 10 carbon atoms, the hydrogen atoms of the methylene groups of which may be substituted by hydrocarbon radicals, and is denoted by- (CR) ³ ₂ ) _c -；R ³ Identical or different at each occurrence and representing a hydrogen atom or a monovalent linear or branched hydrocarbon radical of 1 to 10 carbon atoms, or an aromatic-substituted alkane of 7 to 15 carbon atoms, or an aromatic hydrocarbon radical of 6 to 14 carbon atoms; c is the same or different at each occurrence and is an integer from 1 to 10, preferably methylene (-CH 2-) or n-propyl (-CH 2CH2CH 2-);

a may be the same or different at each occurrence and is 1 or 2 or 3, preferably 2 or 3;

b is not less than 1 and means P ¹ In and-CH ₂ -O-C(＝O)-NH-A-Si(O-R ¹ ) _a R ² _(3-a) The average functionality of the groups to be bonded is an integer or a decimal number, preferably 2 or 3, and more preferably 2.

Preferably, the aforementioned preparation method uses as starting material a component of the general formula:

O＝C＝N-A-Si(O-R ¹ ) _a R ² _(3-a) ] _b (III)

HO-CH ₂ -D-CH ₂ -OH (IV)

P ² (-OH) _b (V)

E(-N＝C＝O) ₂ (VI)

F-CH ₂ -OH (VII)

synthesizing the siloxane-terminated polymer (P) with the structure of formula (I) through three homotypic polymerization reaction steps, wherein the specific preparation steps are as follows:

s1, formula (V) and formula (VI) are reacted, adding a molar excess of formula (VI), i.e. R1= N (NCO, formula VI)/N (OH, formula V) >1 (mol/mol), to prepare a prepolymer P1 terminated with-N = C = O;

s2, adding a molar excess of formula (IV), i.e. R2= n (NCO, P1)/n (OH, formula IV)<1 (mol/mol), preparation with-CH ₂ -an OH terminated prepolymer P2;

s3, adding a calculated amount of formula (III), R3= n (NCO, formula III)/n (OH, P2) (mol/mol), preparing a siloxane-terminated polymer (P) of the structure of formula (I);

s4, after the preparation of the polymer (P), adding a small amount of the component of formula (VII) as a scavenger to scavenge-N = C = O remaining in the above step; this step can improve the storage stability of the siloxane-terminated polymer (P).

In formulae (III) to (VII):

A，a，b，R ¹ and R ² The same as defined in formula (I);

d represents a chemical bond "-" or an oxygen atom or a divalent unit having a number average molecular mass of 14 to 20000g/mol, an ether unit selected from ether linkages, ester linkages or poly-conjugated olefinic linkages, or a polyether unit, or an ester unit, or a polyester unit, or an alkane unit, or a substituted alkane unit, or a cycloalkane unit, or an aromatic hydrocarbon, or an alkene, or a mixture of at least one or more units of polyolefin units. Preferably a chemical bond "-" or an oxygen atom or a hydrocarbon group having a number average molecular weight of 14 to 1000g/mol or an ether group-containing organic substance or polymer segment. In particular, HO-CH may be selected ₂ -CH ₂ -OH，HO-CH ₂ -O-CH ₂ -OH，HO-CH ₂ --CH ₂ -CH ₂ -OH，HO-CH ₂ -CH ₂ -CH ₂ -CH ₂ -OH，HO-(CH ₂ ) ₆ -OH，HO-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OH, or oligo-or polyethers obtained by ring-opening oligomerization or polymerization of oxygen-containing heterocyclic compounds, e.g. polytetramethylene ether glycol, or of the formula (VIII) HO-CH ₂ -CH ₂ -O-P ³ -O-CH ₂ -CH ₂ A compound of-OH, wherein P ³ Is the main chain part of dihydric alcohol or is the ring-opened HO-CH containing epoxy group ₂ -CH ₂ OH-OH is bonded with an ether bond, such as a glycol obtained by condensing 1mol of cyclohexene oxide with 2mol of ethylene glycol, and the like.

Formula (V) is a polyol reactant, is a non-hydrophilic polyol having a number average molecular weight of 1000 to 25000g/mol, is a polyol mixture of at least one or more selected from the group consisting of polyether polyols containing ether linkages, ester linkages or poly-conjugated olefin linkages, polyester polyols and polyolefin polyols, P ² For the polymer portion to which the alcoholic hydroxyl group is attached, polyoxypropylene diol is preferable.

Formula (VI) is a diisocyanate selected from one or a mixture of 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), 4,4' -diphenylmethane diisocyanate (4,4 ' -MDI), 2,4' -diphenylmethane diisocyanate (2,4 ' -MDI), isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4 ' -diisocyanate (H12 MDI), hexamethylene Diisocyanate (HDI), bis- (4-isocyanatocyclohexyl) methane; e represents a unit structure linked to two-N = C = O groups, preferred diisocyanates being: 2,4-toluene diisocyanate (2,4-TDI), isophorone diisocyanate (IPDI) or dicyclohexylmethane-4,4' -diisocyanate (H12 MDI), or Hexamethylene Diisocyanate (HDI);

f is a H atom or a linear, cyclic or branched hydrocarbon radical optionally substituted by heteroatoms and having from 1 to 19 carbon atoms, preferably a hydrogen atom or a methyl radical, i.e. formula (VII) is methanol or ethanol.

In the preparation method, the preparation process can be carried out in batches in a stirring reaction kettle with vacuumizing and heating/cooling functions, and can also be carried out in a continuous production line with a metering pump. The method is preferably carried out in a continuous production line, so that more uniform product quality can be obtained, side reactions are reduced, and the contact chance of a reaction system and air is reduced; the productivity is improved, the exposure chance of the materials in the environment is reduced, the safety and the environmental friendliness are better, and the method is particularly suitable for the continuous preparation of high-viscosity products; the parameter condition of the whole reaction is easier to monitor, and the quality control of the product is better.

Preferably, R1, R2 and R3 and the scavenger of formula (VII) are added in the range: 1< -R1 ≦ 2.2,0.45 ≦ R2<1,0.5 ≦ R3 ≦ 1.5, the monohydric primary alcohol of the structure of formula (VII) may be added in an amount of 0.1 to 0.5 parts based on 100 parts by mass of the polymer polyol of formula (V), and the monohydric alcohol of formula (VII) should be in molar excess of-N = C = O remaining. Before use, the polyoxypropylene ether glycol shown in the formula (V), the dihydric alcohol shown in the formula (IV) and the scavenging agent shown in the formula (VII) are recommended to be subjected to physical or chemical water removal operation, such as conventional polyether polyol water removal processes of stirring and heating to 120 ℃ under vacuum to distill water, molecular sieve water removal, solvent azeotropic water removal and the like, and chemical water removal agents which do not influence the system reaction and the storage stability and the like are added, and the preparation process steps are further briefly described as follows:

step S1, evacuating, stirring and defoaming the polyol having the structure of formula (V) after removing water, replacing the vacuum with an inert gas, adding a certain amount of a urethane formation reaction catalyst, 0.0003 to 0.03 parts by mass of titanium, zirconium, bismuth, zinc, copper, iron or a mixed metal catalyst thereof, and an excess of diisocyanate, wherein the molar ratio R1 is preferably in the range of 1.25:1, the reaction is carried out under normal pressure or under micro-positive pressure protected by inert gas, the reaction temperature is 60-90 ℃, the reaction time is 1-8 hours, the content of isocyanate in the prepolymer generated by the reaction is tested according to a test standard (determination of the content of isocyanate group in the polyurethane prepolymer HG/T2409-1992), when the content of the isocyanate is tested to reach or be slightly lower than a set value, the reaction is ended, the inert gas is continuously introduced for protection, the temperature is reduced to be below 50 ℃, and the steps of vacuumizing and defoaming and replacing vacuum by the inert gas are selected;

in step S2 a diol having a primary hydroxyl end of formula (IV) is added, the molar ratio R2 being the molar ratio of the measured isocyanate content of the prepolymer prepared in S1 to the hydroxyl content of formula (IV) added, preferably R2 being in the range 0.5:1 to 0.75: stirring and reacting at 60-90 ℃ for 1-8 hours under the protection of inert gas, sampling and detecting that the hydroxyl value reaches a set value, or the content of isocyanate is lower than 0.05%, or using FT-IR test-N = C = O, the peak disappears, stopping the reaction, and cooling to below 50 ℃ under the protection of inert gas;

step S3 is performed by adding the isocyanate-containing siloxane end-capping reagent having the structure of formula (III) in a molar ratio of the amount of-N = C = O in the end-capping reagent having the structure of formula (III) to the amount of hydroxyl groups in the hydroxyl-terminated prepolymer obtained in step two, R3 is preferably 0.5:1 to 1.2:1, more preferably 0.98:1 to 1.1:1, in the above range. Stirring and reacting for 1 to 8 hours at 60 to 90 ℃ under the protection of inert gas. Stopping the reaction until the content of-N = C = O of the system reaches a calculated set value, and cooling to below 50 ℃ under the protection of inert gas; vacuumizing, stirring for defoaming, and replacing vacuum with inert gas.

A removing step S4, adding a removing agent with a structure shown in a formula (VII), preferably methanol or ethanol, performing water removing pretreatment on the removing agent by using vinyltrimethoxysilane or vinyltriethoxysilane, and selecting the same alcohol removed from the blocked isocyanate siloxane, the same alcohol removed from the water removing agent and the same removing agent; the proportion range of the water removing agent and the scavenging agent is as follows: 5:1 to 1:5, in an amount of preferably 0.1 to 0.5 parts by mass based on 100 parts by mass of the polymer polyol of the formula (V). Stirring and reacting for 1 to 3 hours at the temperature of between 60 and 90 ℃ under the protection of inert gas, cooling to the temperature below 50 ℃ under the protection of inert gas, and discharging to obtain the siloxane end-capped polymer (P).

Preferably, in the aforementioned formula (I) and formula (III), A-is methylene (-CH) ₂ -) or n-propyl (-CH) ₂ CH ₂ CH ₂ -)，R ¹ Is methyl (-CH) ₃ ) Or ethyl (-CH) ₂ CH ₃ ) The isocyanatosilane of formula (III) is one of the following structures: o = C = N-CH ₂ -Si(O-CH ₃ ) ₃ ，O＝C＝N-CH ₂ -Si(O-CH ₂ CH ₃ ) ₃ ，O＝C＝N-CH ₂ CH ₂ CH ₂ -Si(O-CH ₃ ) ₃ ，O＝C＝N-CH ₂ CH ₂ CH ₂ -Si(O-CH ₂ CH ₃ ) ₃ ，O＝C＝N-CH ₂ -Si(O-CH ₃ ) ₂ (CH ₃ )，O＝C＝N-CH ₂ -Si(O-CH ₂ CH ₃ ) ₂ (CH ₃ )，O＝C＝N-CH ₂ CH ₂ CH ₂ -Si(O-CH ₃ ) ₂ (CH ₃ )，O＝C＝N-CH ₂ CH ₂ CH ₂ -Si(O-CH ₂ CH ₃ ) ₂ (CH ₃ ) The above silanes are all commercially available.

More preferably, the aforementioned polyol reactant formula (V) is a polyoxypropylene ether diol of b =2, having a number average molecular weight of 2000 to 22000g/mol. Known and commercially used polyols can be used. It should be noted that the polyoxypropylene ether glycol selected should have a very low level of unsaturation, so the polymer ends contain predominantly hydroxyl groups. Polyoxypropylene ether glycols of this type are typically prepared by polymerizing propylene oxide using metal complex catalysts, such as double metal hydrides (DMC), having high molecular weights and low levels of unsaturation. The number average molecular weight of the polyoxypropylene ether glycol is preferably from 4000g/mol to 18000g/mol, and the level of unsaturation is less than 0.2, preferably less than 0.01, and more preferably less than 0.008meq/g.

More preferably, formula (VI) is a diisocyanate selected from 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), 4,4' -diphenylmethane diisocyanate (4,4 ' -MDI), 2,4' -diphenylmethane diisocyanate (2,4 ' -MDI), isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4 ' -diisocyanate (H12 MDI), hexamethylene Diisocyanate (HDI), bis- (4-isocyanatocyclohexyl) methane, E represents a unit structure attached to two-N = C = O groups, and in particular the structure shown below can be selected:

further preferably, in the foregoing steps S1 to S4, the reaction temperature is 15 ℃ to 120 ℃, preferably 50 ℃ to 100 ℃, more preferably 60 ℃ to 90 ℃, and the reaction time of each step is 0.5h to 24h, more preferably 1 to 8h, particularly preferably 1.5 to 5 hours: the reaction pressure is 1kPa to 300kPa, preferably 101kPa and is carried out under normal pressure; during the reaction, attention should be paid to isolating moisture and O in the air ₂ By N ₂ Performing atmosphere protection with inert gas such as Ar; it is particularly preferred that the reaction system is evacuated and then replaced with an inert gas under normal pressure, and the inert gas is continuously introduced while isolating the air from the reaction system.

When a relatively high molecular weight polyoxypropylene ether glycol is selected as the reactant polyol of formula (V) to begin the preparation, most of the terminal hydroxyl groups of this type of polyol are secondary hydroxyl groups, and the concentration of hydroxyl groups in the reaction system is relatively low, if no catalyst for urethane formation reaction is added, at the reaction temperature specified in the present invention, the reaction rate is low, the conversion rate is low, and the reaction needs to be carried out at a higher temperature, then allophanate is generated by other side reactions such as-N = C = O and the reaction of amine groups in urethane groups, and polyisocyanate self-polymerizes, so that the viscosity of the whole system increases, the structural control of the polymer is out of control, and the polymerization reaction fails.

Metal tin containing catalysts and tertiary amine catalysts are widely used as catalysts for urethane formation reactions, but these two catalysts are also commonly used catalysts for siloxane hydrolytic crosslinking, which makes the resulting siloxane-terminated polymers sensitive to moisture and affects the storage stability of the polymers. In order to reduce the sensitivity of the polymer to moisture, some acidic substances, such as acyl chloride, benzoic acid and phosphate inhibitors, are required to be added to improve the storage stability of the system, but the addition of the inhibitors also reduces the reactivity of the moisture-curing composition, thereby causing the problems of slow curing and incomplete curing.

The preparation of the inventionThe carbamate-forming reaction in the process does not contain a tin catalyst, the catalyst is one or a mixture of two or more of a titanium-containing catalyst, a zirconium-containing catalyst, a bismuth-containing catalyst, a zinc-containing catalyst, a copper-containing catalyst and an iron-containing catalyst, the amount of the catalyst is at least that of the carbamate-forming reaction, and the amount of the metal titanium, zirconium, bismuth, zinc, copper, iron or a mixture thereof is 0.0003 to 0.03 parts by mass based on 100 parts by mass of the polyol having the structural formula (V). Among the suitable titanium-containing catalysts of the present invention include, but are not limited to, titanium (IV) bis (ethylacetoacetate) diisopropoxide, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, butyl phosphate, titanium complexes of ethanol and isopropanol, and the like, and mixtures thereof. Commercially available titanium-containing catalysts include, but are not limited to: of DorfKetal

PITA,726, TPT,9000, BTM and IAM. Suitable zirconium-containing carbamate-forming reaction catalysts of the present invention include, but are not limited to: bis (cyclopentadienyl) zirconium (IV) dichloride, cyclopentadienyl zirconium (IV) trichloride, tetraacetylzirconium (IV) acetonate, zirconium (IV) tetraacrylate, zirconium (IV) tetrabutoxide, zirconium tetraethoxide, zirconium tetrapropanolate, etc., all commercially available from Aladdin reagent network, sigma-Aldrich (Merck). Suitable bismuth-containing carbamate-forming reaction catalysts of the present invention include, but are not limited to: 2-ethylhexanoic acid ratio, bismuth neodecanoate, bismuth tetramethylheptanedioate, commercially available titanium-containing catalysts include, but are not limited to: of Vertellus holding LLC

83，

28，

16，

Z-22; of Borchers GmbH

Kat 22，

K-of Kat 24, kingindustries

K-348, U-600 by Nitto, and the like. Suitable zinc-containing carbamate-forming reaction catalysts of the present invention include, but are not limited to: zinc acetylacetonate, zinc 2-ethylhexanoate, zinc neodecanoate, and the like, and commercially available zinc-containing catalysts include, but are not limited to: bicatZM from shepherdUSA, octa-SoligenZinc from OMGBorchers, and the like. Suitable iron-containing carbamate-forming reaction catalysts of the present invention include, but are not limited to, iron (III) acetylacetonate, iron monocarboxylates, and the like. Suitable copper-containing carbamate-forming reaction catalysts of the present invention include, but are not limited to, copper (II) acetylacetonate, and the like.

According to the siloxane-terminated polymer (P) disclosed by the invention, the reaction of each step has higher reaction activity through the structural design and process control of the polymer bamboo joint, and the carbamate forming reaction in the whole preparation process can be free of tin catalysts and tertiary amine catalysts. The catalyst used in the present invention is selected from one or a mixture of two or more of a titanium-containing catalyst, a zirconium-containing catalyst, a bismuth-containing catalyst, a zinc-containing catalyst, a copper-containing catalyst, and an iron-containing catalyst, and the amount of the catalyst is at least the amount of the urethane-forming reaction, and 0.0003 to 0.03 parts by mass of a mixed metal catalyst of titanium, zirconium, bismuth, zinc, copper, iron, or the like, preferably 0.0005 to 0.02 parts by mass of the above metal or mixture, more preferably 0.001 to 0.015 parts by mass of the above metal or mixed metal, is used based on 100 parts by mass of the polyol having the structural formula (V).

The present invention also discloses a moisture-curable composition (C) comprising 100 parts by mass of the polymer P according to claim 1, further comprising: 0.1 to 35 parts by mass of a combination selected from the group consisting of a metal-containing catalyst, a guanidine-and imidazole-containing catalyst (C1), and a co-catalyst (C2) comprising a nitrogen-containing silane having a unit structure of the formula (II). The moisture-curing compositions (C) prepared by adding the catalyst combination of C1 and C2, or optionally other components, to the siloxane-terminated polymers (P) in a certain process have very high moisture-curing activity, dry quickly and are completely tack-free.

Preferably, the molar ratio of the group B in the catalyst (C1) to the cocatalyst (C2) is from 10 to 1. Preferably 1:1 to 1:200, more preferably 1:2 to 1:100. the moisture-curing composition (C) of the present invention is preferably added with a combination of the catalyst (C1) and the co-catalyst (C2) in an amount of 0.3 to 35 parts by mass, more preferably 0.5 to 30 parts, based on 100 parts of the silicone-terminated polymer (P).

Among them, the metal-containing catalyst (C1) is preferably a tin-containing or titanium-containing metal catalyst or a catalyst of a mixture thereof. Suitable tin-or titanium-containing metal catalysts of the present invention may be selected from, but are not limited to, titanium (IV) acid esters such as tetrabutyl titanate, tetraisopropyl titanate, bis (ethyl acetoacetate) diisopropoxytitanium, butyl phosphate, titanium complexes of ethanol and isopropanol, and the like; organotin (IV) compounds such as dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin acetylacetonate, dibutyltin oxide, dibutyltin diethylhexanoate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin dimaleate, dioctyltin diacetate, dioctyltin dioctanoate, dioctyltin acetylacetonate, dioctyltin oxide, dioctyltin diethylhexanoate, dioctyltin distearate, complexes of ethyl orthosilicate with dioctyltin or dibutyltin, etc.; stannous (II) catalysts such as stannous octoate, stannous naphthenate, and the like. The catalyst (C1) of the invention may be an amidine, such as 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) or 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU); or guanidines such as 1,3-diphenylguanidine, 1,1,2-trimethylguanidine, 1,1,3,3-tetramethylguanidine, 1,1,2,3,3-pentamethylguanidine, 2-ethyl-1,1,3,3-tetramethylguanidine, 2-butyl-1,1,3,3-tetramethylguanidine.

Specifically, the catalyst (C1) in the present invention is a commercial product. Preference is given to tin-or titanium-containing metal catalysts, particular preference to organotin (IV) catalysts.

The structural formula of the cocatalyst (C2) is shown as formula (II): b is _f Si(O-R ⁴ ) _d R ⁵ _e O _(4-f-d-e)/2 (II)

In formula (II):

the group B, which is the same or different at each occurrence, represents a monovalent, si-C bonded moiety having at least one nitrogen-containing atom that is not bonded to a carbonyl group (-C (= O) -); preferably contains H ₂ N(CH ₂ ) ₃ -、H ₂ N(CH ₂ ) ₂ NH(CH ₂ ) ₃ -and HN (R) ⁴ )-(CH ₂ ) ₃ -(H ₃ CO) ₃ Si(CH ₂ ) ₃ NH(CH ₂ ) ₃ -a group;

R ⁴ represents a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, or a hydrocarbon group containing an alicyclic ring or a substituent of 3 to 20 carbon atoms as an alicyclic ring, or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms or a monovalent hydrocarbon group containing an aromatic group as a substituent, or an alkyl group containing at least one ester energy group, preferably a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a phenyl group, an octyl group or their isomer hydrocarbon groups;

R ⁵ may be the same or different at each occurrence and represents a monovalent Si-C bonded organic moiety containing no N atoms;

f is 0, 1,2,3 or 4;

e is 0, 1,2 or 3;

d is 1,2 or 3;

and d + e + f ≦ 4, and at least one moiety per molecule.

Thus, C2 containing units of the formula (II) may be an amino-containing silane, i.e.d + e + f =4, or an amino-containing oligosiloxane, i.e.d + e + f.ltoreq.3, which amino-containing silane or oligosiloxane also acts as an adhesion promoter in the moisture-curing composition (C).

The following examples of amino group-containing siloxanes may be preferred in the present invention, but are not limited thereto: h ₂ N(CH ₂ ) ₃ -Si(OCH ₃ ) ₃ 、H ₂ N(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₃ 、H ₂ N(CH ₂ ) ₃ -Si(OCH ₃ ) ₂ CH ₃ 、H ₂ N(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₂ CH ₃ 、H ₂ N(CH ₂ ) ₂ NH(CH ₂ ) ₃ -Si(OCH ₃ ) ₃ 、H ₂ N(CH ₂ ) ₂ NH(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₃ 、H ₂ N(CH ₂ ) ₂ NH(CH ₂ ) ₃ -Si(OCH ₃ ) ₂ CH ₃ 、H ₂ N(CH ₂ ) ₂ NH(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₂ CH ₃ 、H ₂ N(CH ₂ ) ₂ NH(CH ₂ ) ₂ NH(CH ₂ ) ₃ -Si(OCH ₃ ) ₃ 、H ₂ N(CH ₂ ) ₂ NH(CH ₂ ) ₂ NH(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₃ 、H ₂ N(CH ₂ ) ₂ NH(CH ₂ ) ₂ NH(CH ₂ ) ₃ -Si(OCH ₃ ) ₂ CH ₃ 、H ₂ N(CH ₂ ) ₂ NH(CH ₂ ) ₂ NH(CH ₂ ) ₃ --Si(OC ₂ H ₅ ) ₂ CH ₃ 、HN(n-C ₄ H ₉ )(CH ₂ ) ₃ -Si(OCH ₃ ) ₃ 、HN(n-C ₄ H ₉ )(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₃ 、HN(n-C ₄ H ₉ )(CH ₂ ) ₃ Si(OCH ₃ ) ₂ CH ₃ 、HN(n-C ₄ H ₉ )(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₂ CH ₃ HN (Ring-C) ₆ H ₁₁ )(CH ₂ ) ₃ -Si(OCH ₃ ) ₃ HN (Ring-C) ₆ H ₁₁ )(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₃ HN (Ring-C) ₆ H ₁₁ )(CH ₂ ) ₃ -Si(OCH ₃ ) ₂ CH ₃ HN (Ring-C) ₆ H ₁₁ )(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₂ CH ₃ 、HN(C ₆ H ₅ )(CH ₂ ) ₃ -Si(OCH ₃ ) ₃ 、HN(C ₆ H ₅ )(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₃ 、HN(C ₆ H ₅ )(CH ₂ ) ₃ -Si(OCH ₃ ) ₂ CH ₃ 、HN(C ₆ H ₅ )(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₂ CH ₃ 、HN[(CH ₂ ) ₃ Si(OCH ₃ ) ₃ ] ₂ 、HN[(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ ] ₂ 、HN[(CH ₂ ) ₃ Si(OCH ₃ ) ₂ CH ₃ ] ₂ 、HN[(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₂ CH ₃ ] ₂ 、HN(n-C ₄ H ₉ )(CH ₂ )-Si(OCH ₃ ) ₃ 、HN(n-C ₄ H ₉ )(CH ₂ )-Si(OC ₂ H ₅ ) ₃ 、HN(n-C ₄ H ₉ )(CH ₂ )Si(OCH ₃ ) ₂ CH ₃ 、HN(n-C ₄ H ₉ )(CH ₂ )Si(OC ₂ H ₅ ) ₂ CH ₃ HN (Ring-C) ₆ H ₁₁ )(CH ₂ )-Si(OCH ₃ ) ₃ HN (Ring-C) ₆ H ₁₁ )(CH ₂ )-Si(OC ₂ H ₅ ) ₃ HN (Ring-C) ₆ H ₁₁ )(CH ₂ )-Si(OCH ₃ ) ₂ CH ₃ HN (Ring-C) ₆ H ₁₁ )(CH ₂ )-Si(OC ₂ H ₅ ) ₂ CH ₃ 、HN(C ₆ H ₅ )(CH ₂ )-Si(OCH ₃ ) ₃ 、HN(C ₆ H ₅ )(CH ₂ )-Si(OC ₂ H ₅ ) ₃ 、HN(C ₆ H ₅ )(CH ₂ )-Si(OCH ₃ ) ₂ CH ₃ 、HN(C ₆ H ₅ )(CH ₂ )-Si(OC ₂ H ₅ ) ₂ CH ₃ And also their partial hydrolysis to give oligomers or copolymers, are preferably commercially available or obtainable by means of preparations customary in chemistry.

As a further preferred, the moisture-curable composition (C) of the present invention further comprises one or more of a crosslinking agent, a water-removing stabilizer, a plasticizer, a filler, a rheology modifier, an adhesion promoter, a pigment, a reinforcing agent, a light stabilizer, a heat stabilizer, and other auxiliaries.

Still more preferably, the moisture-curable composition (C) of the present invention comprises the following components in parts by weight:

(1) 100 parts by mass of a siloxane-terminated polymer (P);

(2) 0.1 to 35 parts by mass of a catalyst (C1) containing metallic tin or metallic titanium and a co-catalyst (C2) having a unit of formula (II), and the molar ratio of the group B in the catalyst (C1) to the co-catalyst (C2) is 10 to 1.

(3) Optionally, 0 to 300 parts by mass of a plasticizer, which is a reactive or non-reactive plasticizer, wherein the non-reactive plasticizer is selected according to the general principle of: (1) in that<Neither reacts with water at 80 ℃ nor with P, C and C2 in components (1), (2); (2) is liquid at 20 ℃ and 101kPa, has a viscosity at 101kPa>A boiling point of 250 ℃; (3) good compatibility in moisture-curable composition (C) and after moisture-curing crosslinking, no precipitation at the use temperature (generally-45 to 80 ℃), polyether having number average molecular weight of 1000g/mol to 6000g/mol such as polyoxypropylene ether; esters such as aromatic esters, alicyclic esters, fatty acid esters, and the like; the reactive diluent is selected from single-head silane terminated polyether with special structure sold in the market, or trimethoxy, triethoxy and dimethoxy silane with 4 to 20 linear alkyl groups; fully esterified aromatic or aliphatic carboxylic acids, fully esterified derivatives of phosphoric acid, fully esterified derivatives of sulfonic acids, branched or unbranchedSaturated hydrocarbons, polystyrene, polybutadiene, polyisobutylene, polyesters, and polyethers. The carboxylic acid ester may be selected from phthalic acid esters such as dioctyl phthalate, diisooctyl phthalate, and diundecyl phthalate, perhydrophthalic acid esters such as 1,2-diisononyl cyclohexanedicarboxylate and 1,2-dioctyl cyclohexanedicarboxylate; adipates, such as dioctyl adipate; benzoic acid esters; esters, glycol esters of trimellitic acid; esters of saturated alkanediols, such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate. Polyethers have polyethylene glycols, poly-THF, and polypropylene glycols with molar masses of preferably 200 to 20 000g/mol. Preference is given to using plasticizers (D) having a molar mass (or, in the case of polymeric plasticizers, an average molar mass Mn) of at least 200g/mol, more preferably greater than 500g/mol, more particularly greater than 900 g/mol. They preferably have a molar mass or an average molar mass Mn of at most 20000g/mol, more preferably at most 10000g/mol, more particularly not more than 8 000g/mol. More preferably, phthalate-free, environmentally friendly plasticizers are used, such as perhydrogenated phthalates, esters of trimellitic acid, polyesters or polyethers. The reactive diluent may be selected from commercially available mono-terminal silane-terminated polyethers of specific structure, for example commercially available up to Wacker chemistry

XM 25 or

XM 20 or other siloxane-terminated polymers having similar structures. Or using trimethoxy, triethoxy, dimethoxysilane with 4 to 20 linear alkyl groups as diluent, one or more mixtures of 1,6-bis- (trimethoxy-silyl) -hexane, 1,8-bis- (methyl-dimethoxy-silyl) -hexyltriethoxysilane, 1,6-bis- (triethoxy-silyl) -hexane, 1,8-bis- (trimethoxy-silyl) -octane, 1,8-bis- (triethoxy-silyl) -octane, 1,8-bis- (methyl-dimethoxy-silyl) -octane can be selected. Octyl trimethoxysilane and dodecane are preferredA methyltrimethoxysilane or a hexadecyltrimethoxysilane.

(4) Optionally, 0 to 20 parts by mass of a water scavenger selected from one or a mixture of more of vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane and methyltriethoxysilane, and an oligomer or copolymer of a partially hydrolyzed oligosiloxane which may contain one or more of the above silanes, the water scavenger also having a cross-linking agent effect in the moisture-curing composition (C);

(5) Optionally, 0-300 parts by mass of methyl silicone resin, phenyl silicone resin and methyl phenyl silicone resin containing methoxy or ethoxy groups are used as reinforcing agents to enhance mechanical properties, heat resistance and weather resistance. The silicone resin used in the present invention may be solid or liquid, preferably liquid, at 23 ℃ and 101 kPa. The silicone resin (B) preferably has a viscosity of 50 to 50000mPas, more preferably 100 to 20 000mPas. The silicone resin may be used in pure form or as a mixture in a suitable solvent. Solvents which can be used here are all compounds which do not react with other components at room temperature and have a boiling point of <250 ℃ at 101 kPa. Ethers (e.g., diethyl ether, methyl tert-butyl ether, ether derivatives of glycols, THF), esters (e.g., ethyl acetate, butyl acetate, glycol esters), aliphatic hydrocarbons (e.g., pentane, cyclopentane, hexane, cyclohexane, heptane, octane, or longer chain branched and unbranched alkanes), ketones (e.g., acetone, methyl ethyl ketone), aromatics (e.g., toluene, xylene, ethylbenzene, chlorobenzene), or alcohols (e.g., methanol, ethanol, glycols, propanol, isopropanol, glycerol, butanol, isobutanol, tert-butanol) may be selected. The silicone resins used in the present invention are commercial products or can be prepared by methods commonly used in silicon chemistry.

(6) Optionally, 0 to 20 parts by mass of a heat-resistant stabilizer, a light stabilizer, an antioxidant or a UV absorbent is selected from more than two of hindered phenols, hindered amines, phosphites, sulfites, salicylates, benzophenones, benzotriazoles, substituted acrylonitriles and triazines for compounding;

(7) Alternatively, 0 to 800 parts by mass of filler, the filler optionally employed may be any desired filler known heretofore. The filler may be selected from non-reinforcing fillers, these being of preferably BET not higher than 50m ² (ii) fillers per gram, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, talc, kaolin, zeolites, metal oxide powders, such as alumina, titanium oxide, iron oxide or zinc oxide, and/or mixed oxides thereof, barium sulfate, ground calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass powders and polymer powders, such as polyacrylonitrile powders; optional reinforcing fillers, these being of greater than 50m ² Fillers with BET surface area, such as pyrogenically prepared fumed silica, precipitated calcium carbonate (light calcium carbonate), carbon blacks, such as furnace black and acetylene black, and mixed silicon aluminum oxides with high BET surface area; aluminum hydroxide, fillers in the form of hollow beads, such as ceramic microbeads, elastic polymer beads, glass beads, or fillers in the form of fibers. By treatment with organosilanes and/or organosiloxanes, or with stearic acid, for example. Preferred fillers are calcium carbonate, talc, aluminum hydroxide, and silica. Preferred types of calcium carbonate are ground or precipitated and optionally surface treated with a fatty acid (e.g., stearic acid) or a salt thereof. The preferred silica is preferably Fumed silica (fused-silica). The fillers (E) optionally employed have a moisture content of preferably less than 1% by weight, more preferably less than 0.5% by weight. It is particularly preferred that the filler is subjected to a conventional water removal treatment such as a preliminary baking treatment in an oven or a liquid material having a high boiling point such as a resin or a plasticizer and being non-reactive with the filler and contained water in a heated vacuum mixer, and the water in the material concerned is vacuum-stirred and distilled at 70 to 150 ℃. If the compositions of the invention comprise fillers, the amount contained is preferably from 80 to 500 parts by weight per 100 parts by weight of siloxane-terminated polymer (P) in each case.

(8) Optionally, 0 to 50 parts by mass of a rheology modifier; such as thixotropic agents (hydrogenated castor oil, polyamide wax powder, fumed silica, etc.) leveling agents, dispersing agents, etc. The thixotropic agent is preferably hydrogenated castor oil, polyamide wax powder, fumed silica, or the like which is a solid compound at room temperature and at a pressure of 101 kPa.

(9) Optionally, 0 to 50 parts by mass of an adhesion promoter, and the cocatalyst C2 may also be used as an adhesion promoter, alone or in combination with a silane coupling agent containing other functional groups, including: mercapto, methacrylate, ureido, urethane, isocyanate, anhydride, or epoxy groups; specific alternatives are, but not limited to: CH (CH) ₂ (O)CHCH ₂ O(CH ₂ ) ₃ Si(OCH ₃ ) ₃ 、CH ₂ (O)CHCH ₂ O(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ 、CH ₂ (O)CHCH ₂ O(CH ₂ ) ₃ Si(OCH ₃ ) ₂ (CH ₃ )、CH ₂ (O)CHCH ₂ O(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₂ (CH ₃ ) 2- (3-triethoxysilylpropyl) maleic anhydride, H ₂ NC(＝O)NH(CH ₂ ) ₃ -Si(OCH ₃ ) ₃ 、H ₂ NC(＝O)NH(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₃ 、H ₂ NC(＝O)NH(CH ₂ ) ₃ -Si(OCH ₃ ) ₂ (CH ₃ )、H ₂ NC(＝O)NH(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₂ (CH ₃ )、H ₂ NC(＝O)NH(CH ₂ )-Si(OCH ₃ ) ₃ 、H ₂ NC(＝O)NH(CH ₂ )-Si(OC ₂ H ₅ ) ₃ 、H ₂ NC(＝O)NH(CH ₂ )-Si(OCH ₃ ) ₂ (CH ₃ )、H ₂ NC(＝O)NH(CH ₂ )-Si(OC ₂ H ₅ ) ₂ (CH ₃ )、H ₃ COC(＝O)NH(CH ₂ ) ₃ -Si(OCH ₃ ) ₃ 、H ₃ COC(＝O)NH(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₃ 、H ₃ COC(＝O)NH(CH ₂ ) ₃ -Si(OCH ₃ ) ₂ (CH ₃ )、H ₃ COC(＝O)NH(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₂ (CH ₃ )、H ₃ COC(＝O)NH(CH ₂ )-Si(OCH ₃ ) ₃ 、H ₃ COC(＝O)NH(CH ₂ )-Si(OC ₂ H ₅ ) ₃ 、H ₃ COC(＝O)NH(CH ₂ )-Si(OCH ₃ ) ₂ (CH ₃ ) 、 H ₃ COC(＝O)NH(CH ₂ )-Si(OC ₂ H ₅ ) ₂ (CH ₃ ) 、H ₅ C ₂ OC(＝O)NH(CH ₂ ) ₃ -Si(OCH ₃ ) ₃ 、 H ₅ C ₂ OC(＝O)NH(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₃ 、H ₅ C ₂ OOC(＝O)NH(CH ₂ ) ₃ -Si(OCH ₃ ) ₂ (CH ₃ ) 、 H ₅ C ₂ OC(＝O)NH(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₂ (CH ₃ ) 、H ₅ C ₂ OC(＝O)NH(CH ₂ )-Si(OCH ₃ ) ₃ 、H ₅ C ₂ OC(＝O)NH(CH ₂ )-Si(OC ₂ H ₅ ) ₃ 、H ₅ C ₂ OC(＝O)NH(CH ₂ )-Si(OCH ₃ ) ₂ (CH ₃ )、H ₅ C ₂ OC(＝O)NH(CH ₂ )-Si(OC ₂ H ₅ ) ₂ (CH ₃ )、HS(CH ₂ ) ₃ Si(OCH ₃ ) ₃ 、HS(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ 、HS(CH ₂ ) ₃ Si(OCH ₃ ) ₂ (CH ₃ )、HS(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₂ (CH ₃ )、CH ₂ ＝C(CH ₃ )C(＝O)O(CH ₂ ) ₃ Si(OCH ₃ ) ₃ 、CH ₂ ＝C(CH ₃ )C(＝O)O(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ 、CH ₂ ＝C(CH ₃ )C(＝O)O(CH ₂ ) ₃ Si(OCH ₃ ) ₂ (CH ₃ )、 CH ₂ ＝C(CH ₃ )C(＝O)O(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₂ (CH ₃ )、CH ₂ ＝C(CH ₃ )C(＝O)O(CH ₂ )Si(OCH ₃ ) ₃ 、 CH ₂ ＝C(CH ₃ )C(＝O)O(CH ₂ )Si(OC ₂ H ₅ ) ₃ 、CH ₂ ＝C(CH ₃ )C(＝O)O(CH ₂ )Si(OCH ₃ ) ₂ (CH ₃ )、 CH ₂ ＝C(CH ₃ )C(＝O)O(CH ₂ )Si(OC ₂ H ₅ ) ₂ (CH ₃ )、CH ₂ ＝CHC(＝O)O(CH ₂ ) ₃ Si(OCH ₃ ) ₃ 、CH ₂ ＝CHC(＝O)O(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ 、CH ₂ ＝CHC(＝O)O(CH ₂ ) ₃ Si(OCH ₃ ) ₂ (CH ₃ )、CH ₂ ＝CHC(＝O)O(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₂ (CH ₃ )、CH ₂ ＝CHC(＝O)O(CH ₂ )Si(OCH ₃ ) ₃ 、CH ₂ ＝CHC(＝O)O(CH ₂ )Si(OC ₂ H ₅ ) ₃ 、CH ₂ ＝CHC(＝O)O(CH ₂ )Si(OCH ₃ ) ₂ (CH ₃ )、CH ₂ ＝CHC(＝O)O(CH ₂ )Si(OC ₂ H ₅ ) ₂ (CH ₃ ) And partially hydrolyzed oligomeric or oligomeric oligomers of the above silanes; o = C = N- (CH) ₂ ) ₃ -Si(OCH ₃ ) ₃ 、O＝C＝N-(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₃ 、O＝C＝N-(CH ₂ ) ₃ -Si(OCH ₃ ) ₂ (CH ₃ )、O＝C＝N-(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₂ (CH ₃ )、O＝C＝N-(CH ₂ )-Si(OCH ₃ ) ₃ 、O＝C＝N-(CH ₂ )-Si(OC ₂ H ₅ ) ₃ 、O＝C＝N-(CH ₂ )-Si(OCH ₃ ) ₂ (CH ₃ )、O＝C＝N-(CH ₂ )-Si(OC ₂ H ₅ ) ₂ (CH ₃ ) And trimeric silanes of the above silanes which are obtained by reaction of NCO groups. Set of the inventionThe compound contains an adhesion promoter, C2 alone or in combination with the above), and then contained in an amount of preferably 0.5 to 30 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the polymer (P).

(10) Other auxiliary agents: one or more of pigments, antibacterial agents and mildew proofing agents.

(11) Optionally, water

In the preparation process, the above components may be mixed in any order to obtain the moisture-curable composition (C) of the present invention. The compositions of the invention can be produced in any known manner, for example by the methods and mixing techniques conventionally used for producing moisture-curing compositions (e.g. room temperature curing one-component silicone sealants, one-component moisture-curing polyurethanes, etc.), the order in which the various ingredients are mixed with one another can also be varied arbitrarily and can be carried out in a continuous or discontinuous production.

The moisture-curing compositions (C) according to the invention are preferably one-component crosslinkable compositions. Alternatively, the composition of the present invention may be part of a two-component crosslinkable system, wherein water (pure or otherwise entrained or reacted to form water) is added to the second component. Or the catalyst C1 and the cocatalyst (C2) and other hydrolysis-active components and low hydrolysis-active components are independently one component, and water (pure water or water carried in another form or water formed by reaction) and the siloxane-terminated polymer (P) having low hydrolysis activity and other low hydrolysis-active components are used as the other component.

The moisture-curing compositions (C) of the invention preferably have a viscous to pasty consistency at 25 ℃ in each case, the viscosity preferably being from 300 to 3000000mPas, more preferably from 500 to 1 500000mPas.

The compositions of the present invention can be stored without water and are crosslinkable when they are in the presence of water. In general, the moisture content of air is sufficient for crosslinking of the moisture-curing composition (C) of the present invention, and therefore the moisture-curing composition (C) of the present invention is preferably crosslinked at room temperature. If desired, crosslinking can also be carried out at temperatures above or below room temperature, such as, for example, at-5 ℃ to 15 ℃ or at 30 ℃ to 50 ℃, and/or by water concentrations above the standard water content of air. The crosslinking is preferably carried out at atmospheric pressure, i.e.at atmospheric pressure of about 90 to 110 kPa.

Thus, the moisture-curable composition (C) of the present invention can be stored without containing water and post-crosslinked to all end uses of the composition of an elastomer upon contact with water at room temperature. Particularly suitable as sealants for joint sealing, including vertical joint sealing, and caulking, for example, of internal width of 10 to 40mm, as in buildings, vehicles, ships and aircraft, or for sealing of roofs, walls or floors, or for frame and perimeter sealing, and for the production of protective coverings, or non-slip coverings or shaped elastic articles, and for insulation of electrical or electronic equipment. The adhesive, the sealant and the coating which are suitable for moisture curing are applied to building bonding, sealing, waterproofing, surface sealing protection, industrial assembly and electronic sealing.

In the prior art, a catalyst containing metallic tin and a tertiary amine catalyst are widely used as catalysts for urethane formation reaction, but the two catalysts are also commonly used for siloxane hydrolysis crosslinking, so that the prepared siloxane-terminated polymer is sensitive to moisture and the storage stability of the polymer is influenced. In order to reduce the sensitivity of the polymer to moisture, some acidic substances, such as acyl chloride, benzoic acid and phosphate inhibitors, are required to be added to improve the storage stability of the system, but the addition of the inhibitors also reduces the reactivity of the moisture-curing composition, thereby causing the problems of slow curing and incomplete curing.

Thus, the invention has the advantages that:

(1) The siloxane end-capped polymer (P) is prepared by three continuous homotypic polymerization reaction steps and one homotypic polymerization reaction cleaning step, the four steps have similar or identical reaction conditions and catalyst selection, and the whole preparation process can be carried out in a non-continuous kettle type reactor or a continuous production line, so that the quality stability of the siloxane end-capped polymer (P) is greatly improved, and end-capped side reaction products are further reduced;

(2) The siloxane-terminated polymer (P) prepared by the invention does not contain catalysts such as organic tin or amine and the like which effectively promote siloxane hydrolysis in the synthetic process, the obtained product has low sensitivity to moisture in air, can be placed for a long time without skinning and obvious thickening, and has excellent storage stability; moreover, the groups participating in the end capping reaction have high activity, a carbamate generation reaction catalyst with high activity for promoting the hydrolysis of the siloxane is not added, and the end capping side reaction products are greatly reduced, so that the siloxane end capping polymer (P) has high end capping rate;

(3) The moisture-curing composition (C) is prepared by adding the catalyst combination of C1 and C2 in the siloxane end-capped polymer (P) or adding other optional components, has very high moisture curing activity, higher hydrolytic crosslinking activity, quick surface drying and complete tack elimination, and is particularly suitable for application of moisture-curing adhesives, sealants and coatings in the fields of building bonding, sealing, waterproofing, surface sealing protection, industrial assembly, electronic packaging, protection and the like.

Detailed Description

The present invention will be described in detail with reference to the following embodiments.

All operations in the following examples were carried out at ambient atmospheric pressure (about 101 kPa) and at room temperature (about 23 ℃ C.) and the crosslinking of the composition was carried out at a relative atmospheric humidity of about 50%, unless otherwise specified.

In the following examples, unless otherwise specified, all the raw materials used were commercially available products or samples (shown in table 1 below), and all the parts were in parts by mass.

Table 1 source of raw materials table

Example 1: preparation of siloxane-terminated polymers (P) by homo-polymerization

3500g of predehydrated DL-12000D polyether polyol (heated at 120 ℃ C. And stirred under vacuum for 2 hours, cooled to room temperature and then treated with N ₂ Protection), adding into a 5L four-neck flask (respectively provided with an anchor stirrer port, a thermometer port, a vacuumizing/nitrogen introducing port and a charging port), thereto was further added 2.0g of a metal titanium-containing catalyst: (

TPT) and 1.5g of a metal-containing bismuth (III) catalyst: (

C716 Stirring and vacuum defoaming with N) ₂ Breaking vacuum and replacing by N ₂ Protection, adding 130.0g IPDI in N ₂ Stirring uniformly under protection, heating in water bath until the temperature of the material is 80-85 ℃, and continuously introducing N ₂ The reaction was protected and maintained for 2 hours.

Sampling, detecting the content of the isocyanate in the prepolymer by a titration method, stopping heating until the content of the isocyanate reaches 0.67 percent, continuing introducing nitrogen to protect, cooling in a cold water bath to below 50 ℃, vacuumizing and defoaming, and using N ₂ Breaking vacuum and replacing by N ₂ Protection (S1);

next, 52.5g BDO was added for N ₂ Protecting, heating in water bath, stirring to 80-85 deg.C, reacting for 4 hr, stopping heating, cooling to below 50 deg.C under nitrogen protection, vacuumizing, defoaming, and adding N ₂ Breaking vacuum and replacing by N ₂ Protection (S2);

then, 133.0g of 3-isocyanato-propyl-trimethoxysilane (A-Link 35) were added for N ₂ Protecting, heating and stirring to 80-85 deg.C, reacting for 4 hr, stopping heating, cooling to below 50 deg.C under nitrogen protection, vacuumizing, defoaming, and adding N ₂ Breaking vacuum and replacing by N ₂ Protection (S3);

finally, 6.5g of scavenger (prepared by A-171 and methanol 1:1 by mass) is added for N ₂ Protecting, heating in water bath, and stirring to 60-70 deg.CAfter 1 hour of reaction, the reaction was checked for absence of isocyanate residue, heating was stopped, and the reaction mixture was cooled to 50 ℃ or lower under nitrogen (S4), whereby the siloxane-terminated polymer (P) of the present example was obtained.

The product obtained in this example is a silicone-terminated polymer (P) which is visually observed as a colorless, transparent, viscous liquid whose viscosity at 25 ℃ is measured as 15000mPas.

In the present embodiment, R1=2, R2=0.5, and R3=1.1.

Example 2: preparation of siloxane-terminated Polymer (P) by Homopolymerization

3500g of predehydrated DL-8000D polyether polyol (heated at 120 ℃ C. And stirred under vacuum for 2 hours, and cooled to room temperature with N ₂ Protection), add a 5L double planetary vacuum stirred tank (XGFJ-8L planetary high speed mixer, equipment manufacturer: doudnerite Automation Equipment Co., ltd.), 1.1g of a catalyst solution containing metallic iron (III) acetylacetonate, 50wt% pre-dissolved in toluene) and 0.9g of a catalyst containing metallic zinc (II) dimethacrylate) were further added thereto, stirred and deaerated by evacuation using N ₂ Breaking vacuum and replacing by N ₂ Protection, addition of 147.7gHDI in N ₂ Stirring uniformly under protection, heating in water bath until the temperature of the material is 80-85 ℃, and continuously introducing N ₂ The reaction was protected and maintained for 2 hours.

Sampling, detecting the content of the isocyanate in the prepolymer by a titration method, stopping heating until the content of the isocyanate reaches 1.01 percent, continuing introducing nitrogen to protect, cooling in a cold water bath to below 50 ℃, vacuumizing and defoaming, and using N ₂ Breaking vacuum and replacing by N ₂ Protection (S1);

next, 41.4g EG were added for N ₂ Protecting, heating in water bath, stirring to 80-85 deg.C, reacting for 4 hr, stopping heating, cooling to below 50 deg.C under nitrogen protection, vacuumizing, defoaming, and adding N ₂ Breaking vacuum and replacing by N ₂ Protection (S2);

then, 101.5g of 3-isocyanato-propyl-trimethoxysilane (A-Link 35) were added for N ₂ Protecting, heating and stirring to 80-85 deg.C, reacting for 4 hr, stopping heating, cooling to 50 deg.C under nitrogen protectionThereafter, N was used in combination with evacuation and defoaming ₂ Breaking vacuum and replacing by N ₂ Protection (S3);

finally, 7.0g of scavenger (prepared by A-171 and methanol 1:1 by mass) is added for N ₂ Protection, heating in water bath and stirring to the material temperature of 60-70 ℃, after 1 hour of reaction, detecting no isocyanate residue, stopping heating, and cooling to below 50 ℃ under the protection of nitrogen (S4), thus obtaining the siloxane end-capped polymer (P) of the embodiment.

The product obtained in this example was a siloxane-terminated polymer (P) having a viscosity of 50000mPas, visually observed at 25 ℃.

In the present embodiment, R1=2, R2=0.67, and R3=1.1.

Example 3: preparation of siloxane-terminated Polymer (P) by Homopolymerization

40kg of a pre-dehydrated DL-8000D polyether polyol (heated at 120 ℃ C. And stirred under vacuum for 2 hours for dehydration, and cooled to room temperature with N ₂ Protection), a 50L double planetary vacuum stirred tank (XGFJ-8L planetary high speed mixer, equipment manufacturer: doctorsil Automation Equipment Co., ltd.), and 40.0g of a metal-zirconium-containing catalyst solution (zirconium (IV) acetylacetonate, 50% by weight dissolved in acetone) and 20.0g of a metal-titanium-containing catalyst (titanium (IV) tetraisopropoxide),

TPT), stirring and vacuum defoaming, using N ₂ Breaking vacuum and replacing by N ₂ Protection, 1.97kg Vestanat H was added ₁₂ MDI in N ₂ Stirring uniformly under protection, heating in water bath until the temperature of the material is 80-85 ℃, and continuously introducing N ₂ The reaction was protected and maintained for 2 hours.

Sampling, detecting the content of the isocyanate in the prepolymer by a titration method, stopping heating until the content of the isocyanate reaches 0.50%, continuing introducing nitrogen to protect, cooling in a cold water bath to below 50 ℃, vacuumizing and defoaming, and using N ₂ Breaking vacuum and replacing by N ₂ Protection (S1);

then 473.8g BDO were added for N ₂ Protection, heating in water bath and stirring to 80-85 deg.C, and reactingHeating for 4 hr, stopping heating, cooling to below 50 deg.C under nitrogen protection, vacuum degassing, and adding N ₂ Breaking vacuum and replacing by N ₂ Protection (S2);

then, 1.30kg of 3-isocyanato-propyl-trimethoxysilane (A-Link 35) was added for N ₂ Protecting, heating and stirring to 80-85 deg.C, reacting for 4 hr, stopping heating, cooling to below 50 deg.C under nitrogen protection, vacuumizing, defoaming, and adding N ₂ Breaking vacuum and replacing by N ₂ Protection (S3);

finally, 40.0g scavenger (methanol) was added for N ₂ Protection, heating in water bath and stirring to the material temperature of 60-70 ℃, after 1 hour of reaction, detecting no isocyanate residue, stopping heating, and cooling to below 50 ℃ under the protection of nitrogen (S4), thus obtaining the siloxane end-capped polymer (P) of the embodiment.

The product obtained in this example was a silicone-terminated polymer (P) which was visually observed as a colorless, transparent, viscous liquid and was tested for a viscosity of 48000mPas at 25 ℃.

In this embodiment, R1=1.5, R2=0.48, and R3=1.15.

Example 4: preparation of siloxane-terminated Polymer (P) by Homopolymerization

3500g of predehydrated DL-12000D polyether polyol (heated at 120 ℃ C. And stirred under vacuum for 2 hours, cooled to room temperature and then treated with N ₂ Protection), add a 5L double planetary vacuum stirred tank (XGFJ-8L planetary high speed mixer, equipment manufacturer: doctorite Automation Equipment Co., ltd.), 40.0g of metal-containing copper (II) catalyst (50 wt% copper (II) diacetone in chloroform) was added thereto, stirred well, vacuum-evacuated to remove the solvent and defoam, and N was used ₂ Breaking vacuum and replacing by N ₂ Protection, adding 130.0g IPDI in N ₂ Stirring uniformly under protection, heating in water bath until the temperature of the material is 80-85 ℃, and continuously introducing N ₂ The reaction was protected and maintained for 2 hours.

Sampling, detecting the content of isocyanate in the prepolymer by a titration method, stopping heating until the content of isocyanate reaches 0.67 percent, continuously introducing nitrogen for protection, cooling in a cold water bath to below 50 ℃, vacuumizing, defoaming andwith N ₂ Breaking vacuum and replacing by N ₂ Protection (S1);

next, 52.7g BDO was added for N ₂ Protecting, heating in water bath, stirring to 80-85 deg.C, reacting for 4 hr, stopping heating, cooling to below 50 deg.C under nitrogen protection, vacuumizing, defoaming, and adding N ₂ Breaking vacuum and replacing by N ₂ Protection (S2);

then, a mixture of 73.1g of 3-isocyanato-propyl-triethoxysilane (T-13) and 73.1g of 3-isocyanato-propyl-methyldimethoxysilane (T-02) was added for N ₂ Protecting, heating and stirring to 80-85 deg.C, reacting for 4 hr, stopping heating, cooling to below 50 deg.C under nitrogen protection, vacuumizing, defoaming, and adding N ₂ Breaking vacuum and replacing by N ₂ Protection (S3);

finally, 2.5g of ethanol and 2.5g of methanol mixed scavenger were added for N ₂ Protection, heating in water bath and stirring to the material temperature of 60-70 ℃, after 1 hour of reaction, detecting no isocyanate residue, stopping heating, and cooling to below 50 ℃ under the protection of nitrogen (S4), thus obtaining the siloxane end-capped polymer (P) of the embodiment.

The product obtained in this example is a dimethoxy and triethoxy silane mixture-terminated polymer which is visually observed as a colorless, transparent, viscous liquid and has a viscosity of 13000mPas at 25 ℃ as measured.

In the present embodiment, R1=2, R2=0.5, and R3=1.1.

Example 5: preparation of siloxane-terminated polymers (P) by homo-polymerization

3500g of predehydrated DL-4000D polyether polyol (heated at 120 ℃ C. And stirred under vacuum for 2 hours, cooled to room temperature and then dehydrated with N ₂ Protection), add a 5L double planetary vacuum stirred tank (XGFJ-8L planetary high speed mixer, equipment manufacturer: doctorsil Automation Equipment Co., ltd.), 3g of a catalyst solution containing metallic iron (III) acetylacetonate, 50wt% pre-dissolved in toluene) was added thereto, stirred and vacuum-defoamed using N ₂ Breaking vacuum and replacing by N ₂ Protection, addition of 190.6g HDI in N ₂ Stirring uniformly under protection, adding in water bathHeating to 80-85 deg.C, and introducing N ₂ The reaction was protected and maintained for 2 hours.

Sampling, detecting the content of the isocyanate in the prepolymer by a titration method, stopping heating until the content of the isocyanate reaches 0.58%, continuing introducing nitrogen to protect, cooling in a cold water bath to below 50 ℃, vacuumizing and defoaming, and using N ₂ Breaking vacuum and replacing by N ₂ Protection (S1);

then, 55.2g of diethylene glycol was added for N ₂ Protecting, heating in water bath, stirring to 80-85 deg.C, reacting for 4 hr, stopping heating, cooling to below 50 deg.C under nitrogen protection, vacuumizing, defoaming, and adding N ₂ Breaking vacuum and replacing by N ₂ Protection (S2);

then, 128.4g of 3-isocyanato-propyl-trimethoxysilane (A-Link 35) were added for N ₂ Protecting, heating and stirring to 80-85 deg.C, reacting for 4 hr, stopping heating, cooling to below 50 deg.C under nitrogen protection, vacuumizing, defoaming, and adding N ₂ Breaking vacuum and replacing by N ₂ Protection (S3);

finally, 5.3g scavenger (methanol) was added, with N being maintained ₂ Protection, heating in water bath and stirring to the material temperature of 60-70 ℃, after 1 hour of reaction, detecting no isocyanate residue, stopping heating, and cooling to below 50 ℃ under the protection of nitrogen (S4) to obtain the siloxane end-capped polymer (P) of the embodiment.

The product obtained in this example was visually observed as a colorless, transparent, viscous liquid, which was tested for a viscosity of 59000mPas at 25 ℃.

In the present embodiment, R1=1.29, R2=0.5, and R3=1.2.

Example 6: preparation of siloxane-terminated Polymer (P) by Homopolymerization

3500g of predehydrated DL-8000D polyether polyol (heated at 120 ℃ C. And stirred under vacuum for 2 hours, and cooled to room temperature with N ₂ Protection), add a 5L double planetary vacuum stirred tank (XGFJ-8L planetary high speed mixer, equipment manufacturer: doudnerite Automation Equipment Co., ltd.), and 3g of a catalyst solution containing metal zirconium (IV) acetylacetonate, 50% by weight pre-dissolved in acetone) was added theretoStirring and vacuum defoaming with N ₂ Breaking vacuum and replacing by N ₂ Protection, addition of 171.3g IPDI, in N ₂ Stirring uniformly under protection, circularly heating in water bath until the temperature of the material is 80-85 ℃, and continuously introducing N ₂ The reaction was protected and maintained for 2 hours.

Sampling, detecting the content of the isocyanate in the prepolymer by a titration method, stopping heating until the content of the isocyanate reaches 0.75%, continuing introducing nitrogen to protect, cooling in a cold water bath to below 50 ℃, vacuumizing and defoaming, and using N ₂ Breaking vacuum and replacing by N ₂ Protection (S1);

then, add 102.1g YT-2187, N sustained ₂ Protection, heating in water bath, stirring to 80-85 deg.C, reacting for 4 hr, stopping heating, cooling to below 50 deg.C under nitrogen protection, vacuumizing, defoaming, and adding N ₂ Breaking vacuum and replacing by N ₂ Protection (S2);

then, 96.2g of 3-isocyanato-propyl-trimethoxysilane (A-Link 35) were added for N ₂ Protecting, heating and stirring to 80-85 deg.C, reacting for 4 hr, stopping heating, cooling to below 50 deg.C under nitrogen protection, vacuumizing, defoaming, and adding N ₂ Breaking vacuum and replacing by N ₂ Protection (S3);

finally, 3g of scavenger (methanol) was added, with N being maintained ₂ Protection, heating in water bath and stirring to the material temperature of 60-70 ℃, after 1 hour of reaction, detecting no isocyanate residue, stopping heating, and cooling to below 50 ℃ under the protection of nitrogen (S4), thus obtaining the siloxane end-capped polymer (P) of the embodiment.

The product obtained in this example was visually observed as a colorless, transparent, viscous liquid, which was tested for a viscosity of 74000mPas at 25 ℃.

In this embodiment, R1=1.75, R2=0.6, and R3=1.05.

Comparative example 1

The preparation method and the main raw materials adopted by the comparative example are the same as those of the example 1. The difference lies in that: this comparative example 1 used a 1L reactor vessel, which was charged at 1/5 of that of example 1, and 0.6g of a metal-containing tin catalyst was used instead of that of example 1Metallic titanium catalyst (A)

TPT) and a metal-containing bismuth (III) catalyst: (

C716 Amount of).

The product obtained in comparative example 1 is a colorless, transparent, viscous liquid, the viscosity of which is measured at 25 ℃ to be 15500mPas.

Comparative example 2

The synthesis procedure was similar with the starting materials and the proportions as in example 3. The only difference being the use of a metallic tin-containing catalyst (dibutyltin dilaurate,

t-12) and a metal titanium-containing catalyst (titanium (IV) tetraisopropoxide,

TPT) instead of the metal zirconium-containing catalyst solution (zirconium (IV) acetylacetonate, 50% by weight dissolved in acetone) and the metal titanium-containing catalyst (titanium (IV) tetraisopropoxide) of example 3,

TPT)。

the specific feeding and process are as follows:

400g of predehydrated DL-8000D polyether polyol (heated at 120 ℃ C. And stirred under vacuum for 2 hours, and cooled to room temperature with N ₂ Protected), a 1L four-necked flask (equipped with an anchor stirrer port, a thermometer port, a vacuum/nitrogen inlet port, and a charging port, respectively) was charged, 0.20g of a metal tin-containing catalyst (dibutyltin dilaurate,

t-12) and 0.20g of a metal-containing titanium catalyst (titanium (IV) tetraisopropoxide,

TPT), stirring and vacuumingVacuum degassing, using N ₂ Puncture vacuum and replace with N2 protection, add 19.7g Vestanat H ₁₂ MDI in N ₂ Stirring uniformly under protection, heating in water bath until the temperature of the material is 80-85 ℃, and continuously introducing N ₂ The reaction was protected and maintained for 2 hours.

Sampling, detecting the content of the isocyanate in the prepolymer by a titration method, stopping heating until the content of the isocyanate reaches 0.50%, continuing introducing nitrogen to protect, cooling in a cold water bath to below 50 ℃, vacuumizing and defoaming, and using N ₂ Breaking the vacuum and replacing with N2 protection (S1);

then, 4.74g BDO was added thereto for N ₂ Protecting, heating and stirring to 80-85 deg.C, reacting for 4 hr, stopping heating, cooling to 50 deg.C to room temperature under nitrogen protection, vacuumizing, defoaming, and adding N ₂ Breaking vacuum and replacing by N ₂ Protection (S2);

then, 13.0g of 3-isocyanato-propyl-trimethoxysilane (A-Link 35) was added for N ₂ Protecting, heating and stirring to 80-85 deg.C, reacting for 4 hr, stopping heating, cooling to 50 deg.C to room temperature under nitrogen protection, vacuumizing, defoaming, and adding N ₂ Breaking vacuum and replacing by N ₂ Protection (S3);

finally, 0.40g scavenger (methanol) was added for N ₂ Protection, heating in water bath and stirring to 60-70 ℃, after 1 hour of reaction, detecting no isocyanate residue, stopping heating, and cooling to 50 ℃ under the protection of nitrogen (S4).

The product obtained is a colorless, transparent, viscous liquid, the viscosity of which is determined to be 50000mPas at 25 ℃.

Comparative example 3

The raw materials and the proportions of the raw materials of the example 4 are fed, and the same synthesis steps are carried out. The only difference being the use of 2.0g of a metallic tin-containing catalyst (dibutyltin dilaurate,

t-12) instead of 4.0g of the metal-containing copper (II) catalyst in example 4 (50% by weight solution of copper (II) diacetone in chloroform).

The product obtained is a colorless, transparent, viscous liquid, the viscosity of which is determined to be 15000mPas at 25 ℃.

Comparative example 4

600g of predehydrated DL-8000D polyether polyol (heated at 120 ℃ C. And stirred under vacuum for 2 hours, and cooled to room temperature with N ₂ Protection), the mixture was charged into a 1L four-necked flask (equipped with an anchor stirrer port, a thermometer port, a vacuum/nitrogen inlet port, and a charging port, respectively), 0.40g of a metal zirconium-containing catalyst solution (zirconium (IV) acetylacetonate, 50wt% dissolved in acetone) and 0.20g of a metal titanium-containing catalyst (titanium (IV) tetraisopropoxide) were charged,

TPT), stirring and vacuum defoaming, using N ₂ Breaking vacuum and replacing by N ₂ Protection; 9.8g of Vestanat H are added ₁₂ MDI in N ₂ After stirring evenly under protection, heating in water bath until the material temperature is 80-85 ℃, continuously introducing N2 for protection and maintaining the reaction for 4 hours.

Sampling, detecting the content of the isocyanate in the prepolymer by a titration method, stopping heating until the content of the isocyanate is 0, continuing introducing nitrogen to protect, cooling in a cold water bath to below 50 ℃, vacuumizing, defoaming and using N ₂ Breaking vacuum and replacing by N ₂ Protection; 17.3g of 3-isocyanato-propyl-trimethoxysilane (A-Link 35) are added for N ₂ And (3) protecting, heating and stirring to the material temperature of 80-85 ℃, reacting for 4 hours, stopping heating, and cooling to below 50 ℃ under the protection of nitrogen.

The final product was a colorless, transparent, viscous liquid, and was tested to have a viscosity of 41000mPas at 25 ℃. The residual isocyanate content was 0.05%.

Comparative example 5

TPT), stirring and vacuum defoaming, using N ₂ Breaking vacuum and replacing by N ₂ Protection, 9.8g of Vestanat H are added ₁₂ MDI in N ₂ Stirring uniformly under protection, heating in water bath until the temperature of the material is 80-85 ℃, and continuously introducing N ₂ The reaction was protected and maintained for 4 hours.

Sampling, detecting the content of the isocyanate in the prepolymer by a titration method, stopping heating until the content of the isocyanate is 0, continuing introducing nitrogen to protect, cooling in a cold water bath to below 50 ℃, vacuumizing, defoaming and using N ₂ Breaking vacuum and replacing by N ₂ Protection; 17.3g of 3-isocyanato-propyl-trimethoxysilane (A-Link 35) were added for N ₂ Protecting, heating and stirring to 80-85 deg.C, reacting for 4 hr, stopping heating, cooling to 50 deg.C to room temperature under nitrogen protection, vacuumizing, defoaming, and adding N ₂ Breaking vacuum and replacing by N ₂ Protection; 0.90g of scavenger (A-171 mixed with methanol 1:1 mass ratio) was added for N ₂ Protection, heating in water bath and stirring to 60-70 deg.C, reacting for 1 hr, detecting no isocyanate residue, stopping heating, and cooling to below 50 deg.C under nitrogen protection.

The final product was a colorless, transparent, viscous liquid, and was tested to have a viscosity of 41000mPas at 25 ℃.

Comparative example 6

600g of predehydrated DL-8000D polyether polyol (heated at 120 ℃ C. And stirred under vacuum for 2 hours, and cooled to room temperature with N ₂ Protected), a 1L four-necked flask (equipped with an anchor stirrer port, a thermometer port, a vacuum/nitrogen inlet port, and a charging port, respectively) was charged, 0.50g of a metal tin-containing catalyst (dibutyltin dilaurate,

t-12), stirring and evacuating for defoaming, using N ₂ Puncture vacuum and replace with N2 protection, add 9.8g Vestanat H ₁₂ MDI in N ₂ Stirring uniformly under protection, heating in water bath to material temperatureThe temperature is between 80 and 85 ℃, and N is continuously introduced ₂ Protecting and maintaining the reaction for 4 hours, sampling, detecting the content of the isocyanate in the prepolymer by a titration method, stopping heating until the content of the isocyanate is 0, continuing introducing nitrogen to cool the prepolymer in a cold water bath to below 50 ℃, vacuumizing and defoaming, and using N ₂ Breaking vacuum and replacing by N ₂ Protection; 17.3g of 3-isocyanato-propyl-trimethoxysilane (A-Link 35) were added for N ₂ Protecting, heating and stirring to 80-85 deg.C, reacting for 4 hr, stopping heating, cooling to 50 deg.C to room temperature under nitrogen protection, vacuumizing, defoaming, and adding N ₂ Breaking vacuum and replacing by N ₂ Protection; 0.90g of scavenger (A-171 mixed with methanol 1:1 mass ratio) was added for N ₂ Protection, heating in water bath and stirring to 60-70 deg.C, reacting for 1 hr, detecting no isocyanate residue, stopping heating, and cooling to below 50 deg.C under nitrogen protection.

Comparative example 7

700.0g of a pre-dehydrated DL-12000D polyether polyol (heated at 120 ℃ C. And dehydrated under vacuum stirring for 2 hours, cooled to room temperature and then treated with N ₂ Protection), a 1L four-neck flask (respectively provided with an anchor stirrer port, a thermometer port, a vacuumizing/nitrogen introducing port and a charging port) was charged, and 0.4g of a catalyst containing metal titanium (a

TPT) and 0.3g of a metal-containing bismuth (III) catalyst: (

C716 Stirring and vacuum defoaming, puncturing vacuum with N2 and replacing with N ₂ Protection, 26.7g of 3-isocyanato-propyl-trimethoxysilane (A-Link 35) are added for N ₂ Protecting, heating and stirring to 80-85 deg.C, reacting for 4 hr, stopping heating, cooling to below 50 deg.C under nitrogen protection, vacuumizing, defoaming, and adding N ₂ Breaking vacuum and replacing by N ₂ Protection; adding 1.3g of scavenging agent (A-171 and methanol 1:1 mass ratio)System), last N ₂ Protection, heating in water bath and stirring to the material temperature of 60-70 ℃, after 1 hour of reaction, detecting no isocyanate residue, stopping heating, and cooling to below 50 ℃ under the protection of nitrogen to obtain the siloxane end-capped polymer (P).

The final product was obtained as a colorless, transparent, viscous liquid, which was tested for a viscosity of 15000mPas at 25 ℃. (R3 = 1.1)

Performance detection

The products of the examples and comparative examples were tested and compared for their properties as follows:

1. evaluation of storage stability of siloxane terminated Polymer

The specific evaluation method comprises the following steps: 100g of a sample to be evaluated is filled into a 200mL open cylindrical container, and the initial viscosity at 25 ℃ is tested, and the storage stability evaluation is performed under the following two conditions, namely, whether the sample is skinned, gelled or solidified, and if the sample is not skinned, gelled or solidified, the viscosity data at 25 ℃ is tested, and the two test conditions are:

(1) Placing in the open at ambient room temperature for 30 days

(2) Placing in a 70 deg.C air-blast oven for 7 days, and standing at room temperature for 4h

If the (1) is not cured or skinned, the product is kept standing at normal temperature for 3 months (90 days).

Test results table 2:

TABLE 2 evaluation of storage stability of siloxane-terminated polymers (units of viscosity: pa.s)

2. Evaluation of the moisture curing Activity of siloxane terminated polymers

The siloxane-terminated polymer/C2/C1 was mixed in 100/2/0.2 parts by mass, in this case C1 was selected to be T-12 and C2 was selected to be Z-6020, and flash mixed and defoamed in a dacsped mixer, and injected into a mold tank made of 50mm x 10mm (L x W x D) polytetrafluoroethylene, according to GB/T13477.5-2002 test method for building sealants part 5: the method described in the determination of surface dry time "selects the surface dry time by finger touch", and after the poured rubber sheet is placed for 24 hours, the tack-free property of the surface of the rubber sheet is tested by the finger touch method, and the test results are shown in table 3:

TABLE 3 evaluation of moisture curing Activity of siloxane terminated polymers

Note: * Surface tack free is characterized by five grades of 1,2,3,4 and 5, 0 representing gel completely without tack free, 1 representing apparent tack, 2 representing surface tacky but capable of being fully cured, 3 representing slight tack, 4 representing surface tack free, substantially tack free, and 5 representing dry surface without any tack.

* With the triethoxysiloxane end-capped polymer of example 4, curing problems occurred with the use of T-12/Z-6020. When the polymer/C1/C2 in example 4 is (P)/U-220H/Z-6020 =100/0.4/2, the tack free time is 25min, the tack free time is 3 hours, and the surface tack free property is 4

Example 7: process for producing moisture-curable composition (C) 1

Fillers used in this example: drying active light calcium CCS-25 and active heavy calcium ML-838C in a forced air oven at 110 deg.C for 12 hr to remove water, and cooling to room temperature.

1000g of the siloxane-terminated polymer (P) from example 2 of the invention, 988.00g of plasticizer DL-2000D, 80.00g of water scavenger A-171 and 20.00g of light stabilizer/UV absorber/heat stabilizer are added to a laboratory 5L double-planetary vacuum stirred tank (XGFJ-8L planetary high-speed stirrer, equipment manufacturer: chengdu silicon Automation Equipment Co., ltd.) equipped with a planetary stirring apparatus and a high-speed dispersing apparatus

B-75, homogenizing at room temperature under low-speed stirring (revolution or planetary stirring speed of 20rpm, dispersion disc speed: 600 rmp) for 3 minutes, introducing cooling water, and mixing 872g of active light calcium CCS-25 and 872.00g of active heavy calcium ML-838C into the body under medium-speed stirring (30 rpm/1500 rpm)In the system, 120.00g of hydrophobic fumed silica is mixed into the system, stirring paddles and floating dust are cleaned, then the system is vacuumized (about 100 mbar) and stirred at a high speed (50 rpm/2500 rpm) for 20 minutes under the condition of cooling water, stirring is stopped, nitrogen is used for puncturing and vacuum replacement, 40.00g of KH-540 and 8.00g of T-12 (of C2 and C1) are added, vacuum pumping (about 100 mbar) and stirring at a medium speed (30 rpm/1500 rpm) for 10 minutes are performed, stirring is stopped, nitrogen is used for puncturing and vacuum replacement; thus, the moisture-curable composition (C) of the present example was obtained and was used as an elastic sealant and an adhesive.

Example 8: process 2 for producing moisture-curable composition (C)

1000g of DINCH plasticizer and light stabilizer were added to a 5L double planetary vacuum stirred tank (XGFJ-8L planetary high-speed stirrer, equipment manufacturer: chengdu silicon Automation Equipment Co., ltd.) equipped with a planetary stirring device and a high-speed dispersing device and equipped with a coiled pipe for steam heating or cooling water introduction

328 and 770, homogenizing at room temperature under low-speed stirring (revolution or planetary stirring speed of 20rpm, dispersion disc speed: 600 rmp) for 3 minutes, mixing 1750g of active light calcium CCS-25, 1250.00g of active heavy calcium ML-838C and 150.00g of titanium dioxide R706 into the system by medium-speed stirring (30 rpm/1500 rpm), cleaning the stirring paddle and floating dust, vacuumizing (about 100 mbar), stirring at high speed (50 rpm/2500 rpm) for 30 minutes, stirring at medium speed (30 rpm/1500 rpm) and vacuumizing, heating the materials to 105-110 ℃ by a steam coil, and carrying out dehydration treatment for 2 hours. Cooling water is introduced into a coil pipe, the temperature of the system is reduced to below 50 ℃ under medium-speed stirring and vacuum pumping, after the nitrogen is broken, 500.00g of the siloxane-terminated polymer (P) in the invention example 1 and 500.00g of the siloxane-terminated polymer (P) in the invention example 3 and 50.00g of the water removing agent A-171 are added, cooling water is introduced into the coil pipe, after the system is homogenized for 20 minutes under high-speed stirring (50 rpm/2500 rpm) by vacuum pumping, after the nitrogen is broken and replaced, 40.00g of Z-6020 and 10.00g of KH-602 (mixed as C2) are added, and after 10.00g of T-12 (C1) is added, after the system is vacuumized (about 100 mbar), the system is stirred for 10 minutes at medium speed (30 rpm/1500 rpm), stirring is stopped, and nitrogen is puncturedBreaking and replacing vacuum; thus, the moisture-curable composition (C) of the present example was obtained and was used as an elastic sealant and an adhesive.

Example 9: process 3 for producing moisture-curable composition (C)

400g of plasticizer DINCH,80.00g of pale gray color paste and 120.00g of thixotropic agent were added to a laboratory 5L double-planetary vacuum stirred tank (XGFJ-8L planetary high-speed stirrer, equipment manufacturer: chengdu silicon Automation Equipment Co., ltd.) equipped with a planetary stirring apparatus and a high-speed dispersing apparatus and having a tube for introducing steam for heating or cooling water

SL, light stabilizer

328 and 770.00 g each, homogenizing at room temperature under low-speed stirring (revolution or planetary stirring speed is 20rpm, dispersion disc speed: 600 rmp) for 3 minutes, mixing 80.00 rutile titanium dioxide R706 and 2000.00g of active triple superphosphate ML-838C into the system by medium-speed stirring (30 rpm/1500 rpm), cleaning the stirring paddle and floating dust, vacuumizing (about 100 mbar), stirring at high speed (50 rpm/2500 rpm) for 30 minutes, stirring at medium speed (30 rpm/1500 rpm) and vacuumizing, heating the material to 105-120 ℃ through a steam coil, and carrying out dehydration treatment for 2 hours. Cooling water is introduced into the coil pipe, the temperature of the system is reduced to below 50 ℃ under the conditions of medium-speed stirring and vacuum pumping, after the nitrogen is broken and replaced, 400.00g of the siloxane-terminated polymer (P) in the embodiment 3 of the invention and 500.00g of the reactive diluent are added

XM 25, 20.00g of water removing agent A-171, introducing cooling water into a coil, vacuumizing and stirring at a high speed (50 rpm/2500 rpm) for 20 minutes, breaking vacuum by nitrogen and replacing, adding 40.00g of KH-540 (C2) and 8.00g of T-12 (C1), vacuumizing (about 100 mbar), stirring at a medium speed (30 rpm/1500 rpm) for 10 minutes, stopping stirring, puncturing by nitrogen and replacing vacuum; that is, the moisture-curable composition (C) of the present example was obtained, benefiting from the reactive diluent

The special effect of XM 25 in lowering modulus can be found in the following information: the moisture-curing compositions (C) of this example, as described in WO2015/024773, have the requirements of 25LM specified in ISO11600 and can be used as building sealants conforming to F-25LM of GB/T14683.

Example 10: process 4 for producing moisture-curable composition (C)

1000.00g of the triethoxysiloxane-terminated polymer (P) of example 4 of the present invention (1000.00 g) and 750.00g of plasticizer DINCH, 12.5g of light stabilizer (DINCH), are added to a laboratory 5L double planetary vacuum stirred tank (XGFJ-8L planetary high-speed stirrer, equipment manufacturer: chengdu silicon Automation Equipment Co., ltd.) equipped with a planetary stirring device and a high-speed dispersing device and equipped with a tube for introducing steam for heating or cooling water

328 and 12.5g

770, homogenizing at room temperature under low speed stirring (revolution or planetary stirring speed is 20rpm, dispersion disc speed: 600 rmp) for 5 minutes, mixing 2000.00 activated light calcium CCS-25 and 1250.00g activated heavy calcium ML-838C and 150.00g titanium dioxide R706 into the system by moderate speed stirring (30 rpm/1500 rpm), cleaning the stirring paddle and floating dust, evacuating (about 100 mbar) under high speed stirring (50 rpm/2500 rpm) for 30 minutes, moderate speed stirring (30 rpm/1500 rpm) and evacuating, heating the material to 105 to 110 ℃ through a steam coil, dehydrating for 2 hours, testing the moisture content below 200ppm, introducing cooling water to the coil, reducing the system to below 50 ℃ under moderate speed stirring and evacuating, breaking and replacing nitrogen, adding 40.00g of Z-6020 and 10.00g of KH-602 (mixing as C2), 15.00g of catalyst U-303H (C1, evacuating and replacing nitrogen and stirring with 1500 rpm) and stopping evacuation after stirring (30 rpm/1500.00 minutes); thus, the moisture-curable composition (C) of the present example was obtained and was used as an elastic sealant and an adhesive.

Comparative example 8

The materials and process of example 9 were used except that the triethoxysiloxane terminated polymer of comparative example 3/DINCH/328/770/CCS-25/ML-838C = 10075 g/75g/1.25g/1.25g/200g/125g was mixed homogeneously using a speedMixer, placed in an oven at 110 ℃ for 2.5 hours, removed and cooled to room temperature. The viscosity rise was found to be significant, with the dispersed gel distributed in the binder after scraping off with a spatula.

Example 11: process for the preparation of two-component moisture-curing compositions (C) 1

1000.00g of the siloxane-terminated polymer (P) of example 5 of the present invention, 80.00g of water scavenger A-171 and 20.00g of light stabilizer/UV absorber/heat stabilizer were added to a 5L double planetary vacuum stirred tank equipped with a planetary stirring apparatus and a high-speed dispersing apparatus (XGFJ-8L planetary high-speed stirrer, equipment Ltd.: chengdu silicon Automation Equipment Co., ltd.)

B-75, homogenizing at low speed at room temperature (revolution or planetary stirring speed is 20rpm, dispersion disc speed is 600 rmp) for 3 minutes, introducing cooling water, mixing 732.00g of active triple superphosphate ML-838C (moisture content is less than 0.1%) into the system by medium speed stirring (30 rpm/1500 rpm), further mixing 120.00g of hydrophobic fumed silica into the system, cleaning stirring paddles and floating dust, introducing cooling water, vacuumizing (about 100 mbar) and stirring at high speed (50 rpm/2500 rpm) for 20 minutes, stopping stirring, puncturing with nitrogen and replacing vacuum, adding 40.00g of KH-540 and 8.00g of T-12 (of C2 and C1), vacuumizing (about 100 mbar), stirring at medium speed (30 rpm/1500 rpm) for 10 minutes, stopping stirring, puncturing with nitrogen and replacing vacuum; that is, the base component K1 of the moisture-curable composition (C) of the present invention is obtained as a thixotropic paste.

588.00g plasticizer DL-2000D, 20.00g purified water, 400g reinforced silicone resin in a laboratory 5L double planetary vacuum stirred tank equipped with a planetary stirrer and a high speed dispersion device (XGFJ-8L planetary high speed stirrer, equipment manufacturer: chengdu silicon Automation Equipment Co., ltd.)

3074 homogenizing at room temperature under low-speed stirring (revolution or planetary stirring speed of 20rpm, dispersion disc speed: 600 rmp) for 3 minutes, mixing 992.00g of active light calcium CCS-25 (not dried and pretreated, water content of about 0.5%) into the system by medium-speed stirring (30 rpm/1500 rpm), cleaning the stirring paddle and floating dust, introducing cooling water, stirring at high speed (50 rpm/2500 rpm) under vacuum (about 100 mbar) for 20 minutes, stopping stirring and releasing vacuum to obtain the moisture-curable composition (C) curing agent K2 which is a thixotropic paste.

The mixing mode of K1 and K2 can be extrusion mixing of the two-component rubber hose in a static mixing head, or mixing in a static mixer and the like, in the embodiment, K1 and K2 are mixed in a DACSpeedMixer before testing and then subjected to glue injection operation, and the mass ratio of K1 to K2 is 1:1 can be cured without water after being mixed uniformly, and is suitable for sealing deep seams and occasions of large-area flat adhesion.

Example 12: process for the preparation of two-component moisture-curing composition (C) 2

1000.00g of the siloxane-terminated polymer (P) of example 4 of the present invention, 800.00g of plasticizer DINCH and 12.5g of photostabilizer were added to a laboratory 5L double planetary vacuum stirred tank (XGFJ-8L planetary high-speed stirrer, equipment manufacturer: kyoto silicon Automation Equipment Co., ltd.) equipped with a planetary stirring device and a high-speed dispersing device

328 and 12.5g

770, homogenizing at room temperature under low-speed stirring (revolution or planetary stirring speed 20rpm, dispersion disc speed 600 rmp) for 3 minutes, introducing cooling water, mixing 1430.00g of active light calcium CCS-25 and 715g of active heavy calcium ML-838C into the system under medium-speed stirring (30 rpm/1500 rpm), mixing 30.00g of hydrophilic fumed silica into the system, cleaning the stirring paddle and floating dust, vacuumizing (about 100 mbar), and stirring at high speed (50 rpm/2500 rpm)) After 20 minutes, the stirring was stopped and the vacuum was released, to obtain a moisture-curable composition (C) of the present invention, i.e., a thixotropic type paste, as the base component K1.

150.00g of plasticizer DINCH is added into a 500mL conical flask with a cover and equipped with magnetic heating stirring, the conical flask is heated to 50 ℃ by magnetic stirring, 15g of cocatalyst (C2) laurylamine A-12 which is melted in advance is added, after uniform magnetic stirring, 35g of catalyst (C1) stannous octoate is added and stirred uniformly, and then continuous stirring is carried out for 1 hour, thus obtaining the curing agent K2 of the moisture-curable composition (C), which is semitransparent liquid.

The mixing mode of K1 and K2 can be uniformly stirred in a stirring kettle or can be carried out in a mixing mode such as mixing in a static mixer, before testing, K1 and K2 are mixed in a DACSpeedMixer and then subjected to glue injection operation, and the mass ratio of K1 to K2 is 20:1, has a working time of 2 to 4 hours after being uniformly mixed, can be cured under the condition of no water, and is suitable for sealing deep seams and occasions of large-area flat pasting adhesion.

Comparative example 9

Substantially the same as in example 11, except that: main component K1 in this comparative example, except that the siloxane-terminated polymer used in comparative example 3, the remainder of the raw materials were mixed in the same ratio to prepare a main component K1. After 2 portions of sealing, one portion was left to stand at room temperature for 30 days and the other portion was left to stand in an oven at 70 ℃ for 7 days, and storage stability evaluations were carried out simultaneously with the K1 component of example 11, and the evaluation results are shown in table 4 below:

	k1-example 12	K2-comparative example 9
			Standing at room temperature for 30 days	No obvious thickening and no gel	The surface is already skinned, and the inside is obviously thickened by the distributed gel
Oven at 70 deg.C for 7 days	No obvious thickening and no gel	Curing

Table 4 storage stability testing comparison of the base component K1

Example 13: process for producing transparent moisture-curable composition (C)

To a laboratory 5L double planetary vacuum stirred tank equipped with a planetary stirring device and a high-speed dispersing device (XGFJ-8L planetary high-speed stirrer, equipment Co., ltd.: chengdu silicon Automation Equipment Co., ltd.), 2100.00g of the siloxane-terminated polymer (P) of example 2 of the present invention, 450.00g of plasticizer DINCH, 54.00g of water scavenger A-171 and 15.00g of light stabilizer/UV absorber/heat stabilizer

B-75, homogenizing at room temperature under low-speed stirring (revolution or planetary stirring speed of 20rpm, dispersion disc speed: 600 rmp) for 3 minutes, introducing cooling water into coil pipe, and stirring at medium speed (30 rpm/1500 rpm) to obtain 150.00g of hydrophilic fumed silica

N20 and 150.00g hydrophobic fumed silica

Mixing H18 into the system, cleaning stirring paddle and floating dust, introducing cooling water, vacuumizing (about 100 mbar), stirring at high speed (50 rpm/2500 rpm) for 20 min, stopping stirring, puncturing with nitrogen gas, replacing vacuum, adding 75.00g KH-540 and 6.00g T-12 (of C2 and C1), vacuumizing (about 100 mbar), stirring at medium speedStirring (30 rpm/1500 rpm) for 10 minutes, stopping stirring, puncturing with nitrogen gas and replacing vacuum; thus, the transparent moisture-curable composition (C) of the present example was obtained and was used as an elastic sealant and an adhesive.

Example 14: moisture-curable composition (C) -Water-resistant coating

In a laboratory 5L double planetary vacuum stirred tank equipped with a planetary stirrer and a high-speed dispersion apparatus (XGFJ-8L planetary high-speed stirrer, equipment Co., ltd.: chengdu silicon Automation Equipment Co., ltd.), 1200.00g of the siloxane-terminated polymer (P) of example 1 of the present invention, 332.00g of an inactive plasticizer DINCH, 600.00g of an active plasticizer dodecyltrimethoxysilane, 80.00g of a water scavenger A-171 and 20.00g of a light stabilizer/UV absorber/heat stabilizer

B-75, homogenizing at room temperature under low-speed stirring (revolution or planetary stirring speed of 20rpm, dispersion disc speed: 600 rmp) for 3 minutes, introducing cooling water into a coil pipe, and stirring at medium speed (30 rpm/1500 rpm) to obtain 40.00g of hydrophobic fumed silica

Mixing H2000, 840.00g superfine aluminium hydroxide and 840g superfine talcum powder into a formula system, cleaning a stirring paddle and floating dust, introducing cooling water, vacuumizing (about 100 mbar) and stirring at a high speed (50 rpm/2500 rpm) for 20 minutes, stopping stirring, puncturing by nitrogen and replacing vacuum, adding 40.00g KH-540 and 8.00g T-12 (of C2 and C1), vacuumizing (about 100 mbar) and stirring at a medium speed (30 rpm/1500 rpm) for 10 minutes, stopping stirring, puncturing by nitrogen and replacing vacuum; thus, the moisture-curable composition (C) of the present invention was obtained as a fluid paste having a viscosity of 13Pa.s, and was useful as a waterproof coating material for sealing the surface of a building.

Performance detection

The products of examples 7-14 were tested for properties and the results are shown in Table 5:

TABLE 5 Performance test results of moisture-curable compositions (C) prepared in examples 7 to 14

It can be seen from the above examples and comparative examples that the siloxane-terminated polymer (P) prepared by the present invention benefits from three homo-type polymerization steps and one homo-type elimination step, so that the functional groups participating in the reaction in each step have higher activity, and the use of a urethane-forming catalyst having a low accelerating effect on the hydrolytic crosslinking of siloxane enables a high conversion rate and a great reduction in the formation of side reaction products, so that it has a high endcapping rate and low water sensitivity, and is excellent in storage stability and simple in storage conditions.

Also benefiting from the homo-polymerization preparation method of the invention, the obtained siloxane-terminated polymer (P) has the advantages of high end-capping rate, low side reaction products and the like, can be quickly cross-linked and cured by moisture or water in the presence of the catalyst C1 and the cocatalyst C2, and can be surface-tack-free.

Meanwhile, when the method of the invention is used for preparing the siloxane-terminated polymer with low hydrolytic crosslinking activity, such as a triethoxy siloxane or dimethoxysiloxane-terminated polymer (P), because a carbamate generating catalyst with low promotion effect on siloxane hydrolytic crosslinking is used, the polymer and the filler can be dehydrated under vacuum heating and stirring, and the production process is the same as that of the traditional moisture curing composition, such as silicone adhesive, so that the production space of the siloxane-terminated polymer is greatly expanded; in addition, in some formulations, such siloxane-terminated polymers can be combined with high moisture content fillers, even with water, for long periods of time without significant hydrolytic crosslinking and curing.

In conclusion, the same type polymerization reaction of the siloxane end-capped polymer can prepare polymers with different viscosities, polymers with different main chain structures and polymers with different siloxane end-capped structures, can improve end-capping efficiency and reduce end-capping side reactions, so that a carbamate generation reaction catalyst with high activity for promoting alkoxy silane hydrolysis can not be added in the synthesis of the siloxane end-capped polymer, and the prepared siloxane end-capped polymer has high end-capping rate, low moisture sensitivity and excellent storage stability. When the common and conventional catalyst, cocatalyst and other related components are added according to a certain proportion to prepare the moisture-cured composition for adhesive, sealant and coating, the composition has high hydrolytic crosslinking activity, can be cured quickly and completely, and has completely tack-free surface. Is particularly suitable for the application fields of adhesives, sealants, coatings, surface sealing, encapsulation, protection and the like; the method is not only suitable for preparing the polyoxypropylene ether polyol, but also suitable for preparing the siloxane end-capped polymer from polyolefin polyol, polyester polyol, other polyether polyol, mixed polyol and the like, thereby greatly expanding the application field of the siloxane end-capped polymer.

The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.

Claims

1. A siloxane end-capped polymer homo-polymerization reaction preparation method is characterized in that the siloxane end-capped polymer (P) has a structure of a formula (I), and components with formulas (III), (IV), (V), (VI) and (VII) are used as raw materials, and continuous or non-continuous preparation is carried out through three homo-polymerization reaction steps and one cleaning reaction step;

P ¹ [-CH ₂ -O-C(=O)-NH-A-Si(O-R ¹ ) _a R ² _(3-a) ] _b （I）

O=C=N-A- Si(O-R ¹ ) _a R ² _(3-a) （III）

HO-CH ₂ -D-CH ₂ -OH (IV)

P ² (-OH) _b （V）

E(-N=C=O) ₂ (VI)

F-CH ₂ -OH (VII)

the preparation steps are as follows:

s2, adding a molar excess of formula (IV), i.e. R2= n (NCO, P1)/n (OH, formula IV)<1 (mol/mol), preparation with-CH ₂ -OH-terminated prepolymer P2;

s3, adding a calculated amount of formula (III), R3= n (NCO, formula III)/n (OH, P2) (mol/mol) to produce siloxane-terminated polymer (P) of formula (I);

s4, after the preparation of polymer (P) is completed, adding the component of formula (VII) as a scavenger to scavenge-N = C = O remaining in the above step;

in formulae (I), (III) to (VII):

P ¹ independently represents a polymer backbone moiety having a number average molecular weight of from 500 to 30000 g/mol; is a b-valent polymer backbone moiety linked via carbon, nitrogen, oxygen;

R ¹ identical or different at each occurrence and represents a monovalent hydrocarbon radical of 1 to 4 carbon atoms;

R ² identical or different at each occurrence and represents a monovalent hydrocarbon radical of 1 to 20 carbon atoms;

a, which is identical or different at each occurrence, represents a divalent hydrocarbon radical of a chain of 1 to 10 carbon atoms, the hydrogen atoms of the methylene groups of which may be substituted by hydrocarbon radicals, and is denoted by- (CR) ³ ₂ ) _c -，R ³ Identical or different at each occurrence and representing a hydrogen atom or a monovalent straight or branched hydrocarbon radical of 1 to 10 carbon atoms, or an aromatic-substituted alkane of 7 to 15 carbon atoms, or an aromatic hydrocarbon radical of 6 to 14 carbon atoms; c is the same or different at each occurrence and is an integer from 1 to 10;

a may be the same or different at each occurrence and is 1 or 2 or 3;

b is not less than 1 and means P ¹ In with-CH ₂ -O-C(=O)-NH-A-Si(O-R ¹ ) _a R ² _(3-a) The average functionality of the groups to which bonding occurs, being an integer or a fraction;

d represents a chemical bond "-" or an oxygen atom or a divalent unit having a number average molecular mass of 14 to 20000g/mol, one or a mixture of several units selected from ether units or polyether units containing ether linkages, ester units or polyester units containing ester linkages, or polyolefin units containing a poly-conjugated olefin linkage;

formula (V) is a polyol reactant, is a non-hydrophilic polyol with the number average molecular weight of 1000 to 25000g/mol, is a polyol mixture of one or more selected from polyether polyol containing ether bonds, polyester polyol containing ester bonds or polyolefin polyol containing poly-conjugated olefin bonds, and P ² Is a polymer moiety attached to an alcoholic hydroxyl group;

the formula (VI) is diisocyanate, and is selected from one or a mixture of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4 '-diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and di- (4-isocyanate cyclohexyl) methane; e represents a unit structure linked to two-N = C = O groups;

f is an H atom or a linear, cyclic or branched hydrocarbon radical optionally substituted by heteroatoms and having from 1 to 19 carbon atoms.

2. The method of claim 1, wherein-A-is methylene-CH in formula I and formula III ₂ -or n-propyl-CH ₂ CH ₂ CH ₂ -，R ¹ Is methyl-CH ₃ Or ethyl-CH ₂ CH ₃ The silane of formula III is a mixture of one or more of the following structures: o = C = N-CH ₂ -Si(O-CH ₃ ) ₃ ，O=C=N-CH ₂ -Si(O-CH ₂ CH ₃ ) ₃ ，O=C=N-CH ₂ CH ₂ CH ₂ -Si(O-CH ₃ ) ₃ ，O=C=N-CH ₂ CH ₂ CH ₂ -Si(O-CH ₂ CH ₃ ) ₃ ，O=C=N-CH ₂ -Si(O-CH ₃ ) ₂ (CH ₃ )，O=C=N-CH ₂ -Si(O-CH ₂ CH ₃ ) ₂ (CH ₃ )，O=C=N-CH ₂ CH ₂ CH ₂ -Si(O-CH ₃ ) ₂ (CH ₃ )，O=C=N-CH ₂ CH ₂ CH ₂ -Si(O-CH ₂ CH ₃ ) ₂ (CH ₃ )。

3. The method of claim 1, wherein the polyoxypropylene ether diol of formula (V) b =2 has a number average molecular weight of 2000-22000 g/mol.

4. The method of claim 1, wherein the amount of R1, R2, and R3 and the scavenger of formula (VII) is in the range of: 1< -R1 ≦ 2.2,0.45 ≦ R2<1,0.5 ≦ R3 ≦ 1.5, the primary monohydric alcohol of the structure of formula (VII) being added in an amount of 0.1 to 0.5 parts based on 100 parts by mass of the polyol reactant of formula (V), and the molar excess of the monohydric alcohol of formula (VII) being such that-N = C = O remains.

5. The method of claim 1, wherein the reaction temperature in the steps S1 to S4 is 15 ℃ to 120 ℃, and the reaction time in each step is 0.5h to 24h: the reaction pressure is 1kPa to 300kPa; moisture and O in the air are isolated in the reaction process ₂ Carrying out atmosphere protection by using inert gas; the carbamate-forming reaction in the preparation process does not contain tin catalyst, the catalyst is one or a mixture of two or more of titanium-containing catalyst, zirconium-containing catalyst, bismuth-containing catalyst, zinc-containing catalyst, copper-containing catalyst and iron-containing catalyst, and the amount of the catalyst is at least the amount of carbamate-forming reaction0.0003 to 0.03 parts by mass of a titanium-containing catalyst, a zirconium-containing catalyst, a bismuth-containing catalyst, a zinc-containing catalyst, a copper-containing catalyst, an iron-containing catalyst or a mixture thereof is used, based on 100 parts by mass of the polyol of formula (V).

6. A moisture-curable composition (C) comprising 100 parts by mass of the polymer (P) according to claim 1, and further comprising: 0.1 to 35 parts by mass of a combination selected from the group consisting of a metal-containing catalyst, a guanidine-and imidazole-containing catalyst (C1), and a co-catalyst (C2) comprising a nitrogen-containing silane having a unit structure of the formula (II):

B _f Si(O-R ⁴ ) _d R ⁵ _e O _(4-f-d-e)/2 （II）

in formula (II):

b is the same or different at each occurrence and represents a moiety having at least one monovalent nitrogen-containing atom not bonded to a carbonyl group and bonded with Si-C;

R ⁴ identical or different at each occurrence and represents a hydrogen atom or a monovalent hydrocarbon radical of 1 to 4 carbon atoms;

f is 0, 1,2,3 or 4;

e is 0, 1,2 or 3;

d is 1,2 or 3;

and d + e + f ≦ 4, and at least one moiety per molecule.

7. The moisture-curable composition (C) according to claim 6, further comprising one or more of a crosslinking agent, a water-removing stabilizer, a plasticizer, a filler, a rheology modifier, an adhesion promoter, a pigment, a reinforcing agent, a light stabilizer, and a heat stabilizer.

8. Moisture-curing composition (C) according to claim 6 or 7, characterized in that it comprises the following components in parts by weight:

(1) 100 parts by mass of a siloxane-terminated polymer (P);

(2) 0.1 to 35 parts by mass of a catalyst (C1) containing metallic tin or metallic titanium and a co-catalyst (C2) having a unit of formula (II), and the molar ratio of the group B in the catalyst (C1) to the co-catalyst (C2) is 10 to 1;

(3) 0 to 300 parts by mass of a plasticizer, which is a reactive or non-reactive plasticizer, wherein the non-reactive plasticizer is selected according to the general principle of: (1) neither reacts with water at <80 ℃ nor with P, C and C2 in components (1), (2); (2) is liquid at 20 ℃ and 101kPa, has a boiling point >250 ℃ at 101 kPa; (3) the moisture-curable composition (C) has good compatibility with the moisture-curable composition (C) after moisture-curable crosslinking, does not cause precipitation at the use temperature, and is a polyether having a number average molecular weight of 1000g/mol to 6000 g/mol; reactive diluents selected from trimethoxy, triethoxy, dimethoxy silane with 4 to 20 straight chain alkyl groups;

(4) 0 to 20 parts by mass of a water scavenger selected from one or a mixture of more of vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane and methyltriethoxysilane, and an oligomer or copolymer of a partially hydrolyzed oligosiloxane containing one or more of the above silanes;

(5) 0-300 parts by mass of methyl silicone resin, phenyl silicone resin and methyl phenyl silicone resin containing methoxy or ethoxy groups as reinforcing agents;

(6) 0 to 20 parts by mass of heat-resistant stabilizer, light stabilizer or antioxidant, and more than two of hindered phenols, hindered amines, phosphites, sulfites, salicylates, benzophenones, benzotriazoles, substituted acrylonitriles and triazines are selected for compounding;

(7) 0 to 800 parts by mass of filler, and one or more of calcium carbonate, alumina, aluminum hydroxide, titanium dioxide and silicon dioxide are selected;

(8) 0 to 50 parts by mass of a rheology modifier;

(9) 0 to 50 parts by mass of an adhesion promoter;

(10) Other auxiliary agents: one or more of pigments, antibacterial agents and mildew proofing agents;

(11) 0 to 20 parts of water.

9. The moisture-curable composition (C) according to claim 8, wherein the components constituting the moisture-curable composition (C) are mixed in an arbitrary order to form one component, or one or more components thereof are independently one or more components to constitute a multi-component curing system.