CN116253889A - Multi-group modified polysiloxane, preparation method and application thereof, and polyurethane foam - Google Patents

Abstract

The invention discloses multi-group modified polysiloxane, a preparation method and application thereof and polyurethane foam, and relates to the technical field of polyurethane rigid foam. The multi-group modified polysiloxane is prepared by adding monoallyl polyoxyethylene ether and a modifier with double ends containing carbon-carbon double bonds to carry out multi-group modification on the basis of polyether modification on low-hydrogen polysiloxane by conventional allyl polyether, so that the problems of coarse cells, high heat conductivity coefficient and the like caused by partial substitution of the bio-based polyol for petroleum-based polyether polyol can be obviously solved, the adding amount of the bio-based polyol can be increased under the condition of the same application effect, and the multi-group modified polysiloxane can be widely applied to the preparation of polyurethane foam as a foam stabilizer under the condition of the same bio-based polyol content.

Description

Multi-group modified polysiloxane, its preparation method, application and polyurethane foam

technical field

The invention relates to the technical field of polyurethane rigid foam, in particular to a multi-group modified polysiloxane, its preparation method, application and polyurethane foam.

Background technique

Due to its low density and low thermal conductivity, rigid polyurethane foam is widely used in household appliances, pipe insulation, refrigerated containers, and construction. In the prior art, polyurethane rigid foam is made up of white material and black material. The main component of the white material is polyether polyol, most of which come from petrochemical or coal chemical products, which are non-renewable resources, and the price is limited by energy price fluctuations. As a renewable resource, there are more and more studies on the preparation of polyols based on bio-based, and researchers have also developed a variety of bio-based polyols.

CN201510660909.4 reports a bio-based polyurethane spray foam. This invention has a high content of bio-based materials, which are applied in the thermal insulation and waterproof spraying of walls or roofs, so that the foam materials have similar properties to foams produced from all petroleum-based materials; CN201810136827.3 reports a bio-based carbonic acid containing Polyurethane with ester structure. The invention has the characteristics of water resistance, heat resistance, etc., and the preparation method is simple and the cost is low.

However, in the process of bio-based polyols replacing traditional polyether polyols in polyurethane foam, researchers also found some problems with bio-based polyols, such as the darker color of polyurethane foam, thicker surface pores of polyurethane foam, and decreased thermal conductivity. , thermal conductivity rise and other phenomena, and even the phenomenon of foam cracking. At present, it is not possible to completely replace petrochemical-based polyethers with bio-based polyols, but to use them in a mixed manner or as a partial replacement.

In order to improve a series of problems such as thicker cells and higher thermal conductivity in the process of partially replacing petrochemical-based polyethers with bio-based polyols, this application is hereby proposed.

Contents of the invention

The object of the present invention is to provide a kind of polygroup modified polysiloxane and its preparation method, application and polyurethane foam.

The present invention is achieved like this:

In the first aspect, the present invention provides a multi-group modified polysiloxane, whose structural formula is

Among them: m=10～60, n=1～10, r=1～4, p=1～3;

R ₁ is selected from any one of methyl, R ₂ , R ₃ and R ₄ ;

The general formula of R ₂ is -CH ₂ CH ₂ CH ₂ O(C ₂ H ₄ O) _a (C ₃ H ₆ O) _b R ₆ , where a=2~30, b=2~15, R ₆ is H Or an alkyl group containing 1 to 4 carbons;

The general formula of R ₃ is -CH ₂ CH ₂ CH ₂ O(C ₂ H ₄ O) _c H, wherein c=3~20;

或-O(C₂H₄O)_d(C₃H₆O)_e-，d＝0～8，e＝0～5，d+e>0或/>

t＝0～15；The general formula of R ₄ is -(CH ₂ ) _x R(CH ₂ ) _x -or -(CH ₂ ) _x R(CH ₂ ) _x-2 CHCH ₂ , x=2~4, the structure of R in the formula:- C _w H _2w -, w=1-5, or

or -O(C ₂ H ₄ O) _d (C ₃ H ₆ O) _e -, d=0~8, e=0~5, d+e>0 or />

t=0～15;

R ₅ is selected from any one of methyl, R ₂ , R ₃ and R ₄ .

In the second aspect, the present invention provides a method for preparing the multi-group modified polysiloxane as described in any one of the foregoing embodiments, which includes: compound containing carbon-carbon double bonds, low-hydrogen-containing polysiloxane The mixture of alkanes, amine additives and solvents can be obtained by reacting under the action of a catalyst.

In a third aspect, the present invention provides the multi-group modified polysiloxane as described in any one of the preceding embodiments or the preparation method of the multi-group modified polysiloxane as described in any one of the preceding embodiments. The obtained multi-group modified polysiloxane is used as a foam stabilizer in the preparation of polyurethane foam.

In a fourth aspect, the present invention provides a polyurethane foam, which includes a polyether polyol, a bio-based polyol and a foam stabilizer, and the mass percentage of the polyether polyol and the bio-based polyol is 50-90%: 10% -50%, the added amount of the foam stabilizer is 1%-3% of the total amount of the polyether polyol and the bio-based polyol, and the foam stabilizer is the polyol described in any one of the preceding embodiments The multi-group modified polysiloxane prepared by the group-modified polysiloxane or the method for preparing the multi-group modified polysiloxane described in any one of the foregoing embodiments.

The present invention has the following beneficial effects:

The multi-group modified polysiloxane provided by the present invention is obtained by adding monoallyl polyoxyethylene ether on the basis of polyether modification of low-hydrogen polysiloxane by conventional allyl polyether Multi-group modification with modified products containing carbon-carbon double bonds at both ends. The multi-group modified polysiloxane of the present application brings more plasticity in structure, and the corresponding groups in the structure can be adjusted according to different types of bio-based polyols. This modified polysiloxane can significantly improve the problems of coarse cells and high thermal conductivity caused by partial substitution of petroleum-based polyols by bio-based polyols. Under the same application effect, it can increase the amount of bio-based polyols added. Under the same bio-based polyol content, its application performance is better. The multi-group modified polysiloxane provided by the present invention is widely applicable to the preparation of polyurethane foam as a foam stabilizer, and the polyurethane foam added with multi-group modified polysiloxane is partially replaced by bio-based polyols for petrochemical-based polyols However, the problems of thicker cells and higher thermal conductivity have been well improved, and the reduction of closed cell ratio, parallel compressive strength and vertical compressive strength reduction rate have all been improved.

Detailed ways

In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be purchased from the market.

The invention provides a multi-group modified polysiloxane, whose structural formula is

Among them: m=10～60, n=1～10, r=1～4, p=1～3;

R ₁ is selected from any one of methyl, R ₂ , R ₃ and R ₄ ;

The general formula of R ₂ is -CH ₂ CH ₂ CH ₂ O(C ₂ H ₄ O) _a (C ₃ H ₆ O) _b R ₆ , where a=2~30, b=2~15, R ₆ is H Or an alkyl group containing 1 to 4 carbons;

The general formula of R ₃ is -CH ₂ CH ₂ CH ₂ O(C ₂ H ₄ O) _c H, wherein c=3~20;

或-O(C₂H₄O)_d(C₃H₆O)_e-，d＝0～8，e＝0～5，d+e>0或/>

t＝0～15；The general formula of R ₄ is -(CH ₂ ) _x R(CH ₂ ) _x -or -(CH ₂ ) _x R(CH ₂ ) _x-2 CHCH ₂ , x=2~4, the structure of R in the formula:- C _w H _2w -, w=1-5, or

or -O(C ₂ H ₄ O) _d (C ₃ H ₆ O) _e -, d=0~8, e=0~5, d+e>0 or />

t=0～15;

R ₅ is selected from any one of methyl, R ₂ , R ₃ and R ₄ .

其中/>

用M^E表示。Preferably, the structural formula of _R is expressed as:

where />

Expressed in ^ME .

Further, the present invention also provides a method for preparing the above-mentioned multi-group modified polysiloxane, which comprises the following steps:

(1) Preparation of low hydrogen-containing polysiloxane.

Low-hydrogen-containing polysiloxane can be purchased commercially, or can be prepared independently. The preparation method is: using hexamethyldisiloxane, octamethylcyclotetrasiloxane and high-hydrogen-containing polysiloxane as raw materials, in Under the acidic catalyst, react at 60°C for 8 hours to prepare low-hydrogen polysiloxane. Among them, the acid catalyst is acid clay.

In the present application, different types of low-hydrogen-containing polysiloxanes can be obtained by adjusting the ratio of raw materials hexamethyldisiloxane, octamethylcyclotetrasiloxane and high-hydrogen-containing polysiloxane, such as It can be MD ₄₀ D' ₅ M, MD ₃₅ D' ₇ M, MD ₅₀ D' ₈ M, wherein, according to the specific type of low hydrogen-containing polysiloxane Adjusting the dosage ratio of tetrasiloxane and high hydrogen-containing polysiloxane is a conventional technology, which will not be elaborated in this application.

(2) Preparation of compounds containing carbon-carbon double bonds.

Compounds containing carbon-carbon double bonds include allyl polyethers, monoallyl polyoxyethylene ethers, and compounds containing carbon-carbon double bonds at both ends.

Among them, allyl polyether realizes polyether modification of polysiloxane, and the average molecular weight of allyl polyether is 1000-1500; allyl polyether contains ethylene oxide with a mole percentage of 60%-80%. Oxy group, terminating in a hydroxyl or methyl group.

The average molecular weight of monoallyl polyoxyethylene ether is 200-400;

The modified product containing carbon-carbon double bonds at both ends includes at least one of diallyl polyether, polysiloxane with carbon-carbon double bonds at both ends, diene at the end and bisphenol A diallyl ether polyether species; preferably, the polysiloxane containing carbon-carbon double bonds at both ends is vinyl-terminated polydimethylsiloxane. The vinyl-terminated polydimethylsiloxane can be purchased commercially or can be self-made. The preparation method is to add octamethylcyclotetrasiloxane and tetramethyldivinyldisiloxane to the reactor, Under the action of clay, react at 70°C for 5 hours to obtain vinyl-terminated polydimethylsiloxane, which can be obtained by adjusting the ratio of raw materials octamethylcyclotetrasiloxane and tetramethyldivinyldisiloxane Different models of vinyl-terminated polydimethylsiloxane, such as M ^E D ₁₀ M ^E , M ^E D ₈ M ^E , wherein, according to the specific model of vinyl-terminated polydimethylsiloxane on the raw material It is a conventional technique to adjust the proportion of the dosage, and the present application will not elaborate on it again.

Preferably, the mass ratio of allyl polyether, monoallyl polyoxyethylene ether and the compound containing carbon-carbon double bonds at both ends is 200-250:4-9:1-3.

(3) The mixture of compounds containing carbon-carbon double bonds, low-hydrogen polysiloxane, amine additives and solvents is reacted under the action of a catalyst.

Specifically, compounds containing carbon-carbon double bonds, low-hydrogen polysiloxanes, and solvents are fed according to a mass ratio of 205-262:50-90:40-50; the amount of amine additives accounts for The concentration in parts per million is 80-120ppm; the above-mentioned compound containing carbon-carbon double bond, low hydrogen-containing polysiloxane, amine additives and solvent are mixed uniformly to obtain a mixture, and the mixture is stirred in a nitrogen atmosphere, and the temperature is raised to 85-105°C, keep warm for 0.5-1h, then add catalyst (the amount of catalyst is 8-12ppm per million of the total feeding amount), keep warm for 5-7h, and remove the remaining solvent in the mixture.

Preferably, the amine additives include at least one of N,N-dimethylethanolamine, N,N-dibutylethanolamine, 3-dimethylpropylamine and 2-butylaminoethanol; more preferably, the amine The auxiliary agent is NN-dimethylethanolamine; the solvent is isopropanol or toluene. The catalyst is a palladium-containing complex, a rhodium-containing complex or a platinum-containing complex; more preferably, the catalyst is chloroplatinic acid.

In this application, on the basis of polyether modification of low hydrogen-containing polysiloxane by conventional allyl polyethers, monoallyl polyoxyethylene ethers and double-end groups containing carbon-carbon double bonds are added. Modifiers undergo multi-group modification. The multi-group modified polysiloxane of the present application brings more plasticity in structure, and the corresponding groups in the structure can be adjusted according to different types of bio-based polyols. This modified polysiloxane can significantly improve the problems of coarse cells and high thermal conductivity caused by partial substitution of petroleum-based polyols by bio-based polyols. Under the same application effect, it can increase the amount of bio-based polyols added. Under the same bio-based polyol content, its application performance is better. The invention is widely applicable to industries such as home appliances and plates.

In addition, the present application also provides the application of the above-mentioned multi-group modified polysiloxane as a foam stabilizer in the preparation of polyurethane foam. The multi-group modified polysiloxane of the present application can especially be used in polyurethane foams in which bio-based polyols partially replace petrochemical-based polyethers as a foam stabilizer, which can improve the There are a series of problems such as thicker cells and higher thermal conductivity.

For example, the present application correspondingly provides a polyurethane foam, which includes petroleum-based polyether polyol, bio-based polyol and foam stabilizer, the mass percentage of polyether polyol and bio-based polyol is 50-90%: 10% -50%, the added amount of the foam stabilizer is 1%-3% of the total amount of petroleum-based polyether polyol and bio-based polyol, and the foam stabilizer is the above-mentioned multi-group modified polysiloxane.

Polyurethane foam added with multi-group modified polysiloxane has been well improved, such as the thickening of cells and the increase of thermal conductivity caused by the partial substitution of bio-based polyols for petrochemical-based polyethers, and the closed cell rate is reduced and parallel Both compressive strength and vertical compressive strength reduction rate were improved. Under the same application effect, the added amount of bio-based polyol can be increased, and under the same content of bio-based polyol, its application performance is better.

The characteristics and performance of the present invention will be described in further detail below in conjunction with the examples.

Example 1

This example provides a multi-group modified polysiloxane, the preparation method of which comprises: adding 210.0 g of olefin with an average molecular weight of 1000 to a round bottom flask equipped with a mechanical stirrer, a dry nitrogen line and a reflux condenser. Propyl starting polyether (the polyether contains 80% by mole of ethyleneoxy groups and terminated with hydroxyl groups), 9.0g of monoallyl polyoxyethylene ether with an average molecular weight of 400, 1.0g1, 8-nonadiene, 90.0g low hydrogen polysiloxane (MD ₄₀ D' ₅ M), 50g isopropanol, 100ppm N,N-dimethylethanolamine. Stir the mixture in a nitrogen atmosphere, heat up to 85-90°C, keep warm for 0.5h, add 10ppm chloroplatinic acid, keep warm for 6h, remove the solvent, and obtain a clear and transparent light brown liquid, which is polygroup modified polysiloxane .

Example 2

This example provides a multi-group modified polysiloxane, the preparation method of which comprises: adding 250.0 g of olefin with an average molecular weight of 1500 to a round bottom flask equipped with a mechanical stirrer, a dry nitrogen line and a reflux condenser. Propyl starting polyether (the polyether contains 60% by mole of ethyleneoxy groups and terminated with hydroxyl groups), 4.0g monoallyl polyoxyethylene ether with an average molecular weight of 200, 1.0g1, 7-octadiene, 50.0g low hydrogen polysiloxane (MD ₃₅ D' ₇ M), 50g isopropanol, 100ppm N,N-dimethylethanolamine. Stir the mixture in a nitrogen atmosphere, heat up to 85-90°C, keep warm for 0.5h, add 10ppm chloroplatinic acid, keep warm for 6h, remove the solvent, and obtain a clear and transparent light brown liquid, which is polygroup modified polysiloxane .

Example 3

This example provides a multi-group modified polysiloxane, the preparation method of which comprises: adding 210.0 g of olefin with an average molecular weight of 1000 to a round bottom flask equipped with a mechanical stirrer, a dry nitrogen line and a reflux condenser. Propyl starting polyether (the polyether contains 80 mole percent ethyleneoxy groups, terminated with methyl groups), 4.0 g Monoallyl polyoxyethylene ether with an average molecular weight of 200, 2.0 g Bisphenol A diallyl ether, 90.0g low hydrogen polysiloxane (MD ₄₀ D' ₅ M), 50g isopropanol, 100ppm N,N-dimethylethanolamine. Stir the mixture in a nitrogen atmosphere, heat up to 85-90°C, keep warm for 0.5h, add 10ppm chloroplatinic acid, keep warm for 6h, remove the solvent, and obtain a clear and transparent light brown liquid, which is polygroup modified polysiloxane .

Example 4

This example provides a multi-group modified polysiloxane, the preparation method of which comprises: adding 220.0 g of olefin with an average molecular weight of 1000 to a round bottom flask equipped with a mechanical stirrer, a dry nitrogen line and a reflux condenser. Propyl starting polyether (the polyether contains 80% by mole of ethyleneoxy groups, terminated by hydroxyl groups), 8.0 g of monoallyl polyoxyethylene ether with an average molecular weight of 400, 3.0 g of average Molecular weight is the bisallyl polyether of 400 (this polyether contains the ethylene oxide group that molar percentage is 80%), 80.0g gained low hydrogen polysiloxanes (MD ₅₀ D ' ₈ M), 40g toluene , 100ppm N,N-dimethylethanolamine. Stir the mixture in a nitrogen atmosphere, heat up to 85-90°C, keep warm for 0.5h, add 10ppm chloroplatinic acid, keep warm for 6h, remove the solvent, and obtain a clear and transparent light brown liquid, which is polygroup modified polysiloxane .

Example 5

This example provides a multi-group modified polysiloxane, the preparation method of which comprises: adding 200.0 g of olefin with an average molecular weight of 1000 to a round-bottomed flask equipped with a mechanical stirrer, a dry nitrogen line, and a reflux condenser. Propyl starting polyether (the polyether contains 80 mole percent ethyleneoxy groups terminated with hydroxyl groups), 8.0 g of monoallyl polyoxyethylene ether with an average molecular weight of 400, 3.0 g of terminal Vinyl polydimethylsiloxane ( ^ME D ₁₀ M ^E ), 80.0 g low hydrogen polysiloxane (MD ₄₀ D' ₅ M), 40 g toluene, 100 ppm N,N-dimethylethanolamine. Stir the mixture in a nitrogen atmosphere, heat up to 100-110°C, keep warm for 1h, add 10ppm chloroplatinic acid, keep warm for 6h, remove the solvent, and obtain a clear and transparent light brown liquid, which is polygroup modified polysiloxane.

Example 6

This example provides a multi-group modified polysiloxane, the preparation method of which comprises: adding 240.0 g of olefin with an average molecular weight of 1200 to a round-bottomed flask equipped with a mechanical stirrer, a dry nitrogen line, and a reflux condenser. Propyl starting polyether (the polyether contains 80 mole percent ethyleneoxy groups terminated with hydroxyl groups), 8.0 g of monoallyl polyoxyethylene ether with an average molecular weight of 200, 2.0 g of terminal Vinyl polydimethylsiloxane (ME ^D ₈ M ^E ), 50.0 g of the obtained low hydrogen polysiloxane (MD ₃₅ D' ₇ M), 40 g of toluene, 100 ppm N,N-dimethylethanolamine. Stir the mixture in a nitrogen atmosphere, raise the temperature to 100-110°C, keep it warm for 0.5h, add 10ppm chloroplatinic acid, keep it warm for 6h, remove the solvent, and get a clear and transparent light brown liquid, which is the multi-group modified polysiloxane .

Comparative example 1

This comparative example provides a modified polysiloxane, the preparation method of which is basically the same as that of Example 1, the only difference being that some raw materials in Example 1 are omitted: 9.0 g of monoallyl polysiloxane with an average molecular weight of 400 Oxyethylene ether, 1.0 g 1,8-nonadiene and 50 g isopropanol.

The specific preparation method is as follows: Add 210.0 g of allyl starting polyether with an average molecular weight of 1000 (this polyether contains 80% mole percent of ethyleneoxy group, the terminal is a hydroxyl group), 90.0 g low hydrogen polysiloxane (MD ₄₀ D' ₅ M), 100 ppm N,N-dimethylethanolamine. Stir the mixture in a nitrogen atmosphere, raise the temperature to 85-90°C, keep it warm for 0.5h, add 10ppm chloroplatinic acid, keep it warm for 6h, and obtain a clear and transparent light brown liquid, which is the modified polysiloxane.

Comparative example 2

This comparative example provides a modified polysiloxane, the preparation method of which is basically the same as that of Example 2, the only difference being that some raw materials in Example 2 are omitted: 4.0 g of monoallyl polysiloxane with an average molecular weight of 200 Oxyethylene ether, 1.0 g 1,7-octadiene and 50 g isopropanol.

The specific preparation method is as follows: add 250.0 g of allyl starting polyether with an average molecular weight of 1500 (this polyether contains 60% mole percent of ethyleneoxy group, the terminal is a hydroxyl group), 50.0 g of low hydrogen polysiloxane (MD ₃₅ D' ₇ M), 100 ppm N,N-dimethylethanolamine. Stir the mixture in a nitrogen atmosphere, raise the temperature to 85-90°C, keep it warm for 0.5h, add 10ppm chloroplatinic acid, keep it warm for 6h, and obtain a clear and transparent light brown liquid, which is the modified polysiloxane.

Comparative example 3

This comparative example provides a modified polysiloxane, the preparation method of which is basically the same as that of Example 3, the only difference being that some raw materials in Example 3 are omitted: 4.0 g of monoallyl polysiloxane with an average molecular weight of 200 Oxyethylene ether, 2.0g bisphenol A diallyl ether, 50g isopropanol.

The specific preparation method is as follows: Add 210.0 g of allyl starting polyether with an average molecular weight of 1000 (this polyether contains 80% mole percent of ethyleneoxy group, methyl end), 90.0 g low hydrogen polysiloxane (MD ₄₀ D' ₅ M), 100 ppm N,N-dimethylethanolamine. Stir the mixture in a nitrogen atmosphere, heat up to 85-90°C, keep warm for 0.5h, add 10ppm chloroplatinic acid, keep warm for 6h, remove the solvent, and obtain a clear and transparent light brown liquid, which is polygroup modified polysiloxane .

Comparative example 4

This comparative example provides a modified polysiloxane, the preparation method of which is basically the same as in Example 4, the only difference being that 8.0 g of monoallyl polyoxyethylene with an average molecular weight of 400 in Example 4 is omitted Base ether, 3.0 g of bisallyl polyether with an average molecular weight of 400 (the polyether contains 80 mole percent ethyleneoxy groups), and 40 g of toluene as a solvent was also omitted.

The specific preparation method is as follows: Add 220.0 g of allyl starting polyether with an average molecular weight of 1000 (this polyether contains 80% by mole percent) in a round bottom flask equipped with a mechanical stirrer, dry nitrogen pipeline and reflux ethyleneoxy group, the terminal is a hydroxyl group), 80.0 g of the obtained low hydrogen polysiloxane (MD ₅₀ D' ₈ M), 100 ppm N,N-dimethylethanolamine. Stir the mixture in a nitrogen atmosphere, raise the temperature to 85-90°C, keep it warm for 0.5h, add 10ppm chloroplatinic acid, keep it warm for 6h, and obtain a clear and transparent light brown liquid, which is the modified polysiloxane.

Comparative example 5

This comparative example provides a modified polysiloxane, the preparation method of which is basically the same as that of Example 6, the only difference being that some raw materials in Example 6 are omitted: 8.0 g of monoallyl polysiloxane with an average molecular weight of 200 Oxyethylene ether, 2.0g vinyl-terminated polydimethylsiloxane (ME ^D ₈ M ^E ), 40g toluene.

The specific preparation method is as follows: the specific preparation method is as follows: add 240.0 g of allyl starting polyether with an average molecular weight of 1200 (this polyether contains mole The percentage is 80% ethyleneoxy group, the terminal is hydroxyl group), 50.0 g low hydrogen polysiloxane (MD ₃₅ D' ₇ M), 100 ppm N,N-dimethylethanolamine. Stir the mixture in a nitrogen atmosphere, raise the temperature to 100-115°C, keep it warm for 0.5h, add 10ppm chloroplatinic acid, keep it warm for 6h, and obtain a clear and transparent light brown liquid, which is the modified polysiloxane.

Carry out application evaluation to described embodiment and comparative example, mix polyurethane white material according to the following table, and carry out application evaluation comparison.

Table 1 Polyurethane white material component part parameters (mass ratio)

raw material Matching ratio 1 Matching 2 Matching ratio 3 Polyether polyol A 100 70 50 Bio-Based Polyol B 0 30 50 foam stabilizer 2.0 2.0 2.0

Polyether polyol A is a polyether polyol starting from sucrose, with a hydroxyl value of 380 mgKOH/g and a hydroxyl functionality of 6;

Bio-based polyol B is epoxidized soybean oil-based vegetable oil polyol with a hydroxyl value of 310 mgKOH/g and a hydroxyl functionality of 4.5.

Perform performance tests on the rigid polyurethane foam obtained above, wherein, the determination of thermal conductivity refers to "GB/T10295-2008 Determination of steady-state thermal resistance and related characteristics of thermal insulation materials", and the determination of closed cell rate refers to "GB/T 10799- 2008 "Determination of Open Cell and Closed Cell Volume Percentage of Rigid Foam Plastics", the compression strength test of rigid polyurethane foam refers to "GB 8813-88 Compression Test Method for Rigid Foam Plastics", where the parallel compression strength refers to the pressure parallel to the growth direction of the foam Direction, vertical compressive strength refers to the direction perpendicular to the pressure and foam growth direction.

Table 2 Proportion 1 prepares rigid polyurethane foam application performance test results

Table 3 Proportion 2 prepares rigid polyurethane foam application performance test results

Table 4 Proportion 3 Prepares Rigid Polyurethane Foam Application Performance Test Results

It can be seen from Table 2 that the properties of rigid polyurethane foams are not much different without using bio-based polyols. Table 3 and Table 4 show that after adding bio-based polyols, it can be seen from the performance test results of each rigid polyurethane foam that the conventional modified polysiloxane has obvious differences in foam performance, the thermal conductivity increases, and the closed cell ratio decreases; The distribution of cells is not uniform, and the difference between parallel compressive strength and vertical compressive strength becomes larger. Comparing the data of Examples 1-6 and Comparative Examples 1-5 in Table 3 and Table 4, it can be seen that the rate of increase in thermal conductivity in Examples 1-6 is far less than that of Comparative Examples 1-5, and the more thermal conductivity increases, The thermal conductivity will decrease accordingly. At the same time, the decrease of the closed cell ratio in Examples 1-6 is much smaller than that of Comparative Examples 1-5, and the increase of the difference between parallel compressive strength and vertical compressive strength in Examples 1-6 is much smaller than that of Comparative Examples 1-5. The above data shows that under the same application effect, the multi-group modified polysiloxane of the present invention can significantly increase the amount of bio-based polyol added, and its application performance is better under the same bio-based polyol content.

In summary, the multi-group modified polysiloxane provided by this application is modified by adding monoallyl poly Oxyethylene ether and modified products containing carbon-carbon double bonds at both ends are subjected to multi-group modification, and the obtained multi-group modified polysiloxane has monoallyl polyoxyethylene ether in the molecule and dienyl species. The multi-group modified polysiloxane of the present application brings more plasticity in structure, and the corresponding groups in the structure can be adjusted according to different types of bio-based polyols. This modified polysiloxane can significantly improve the problems of coarse cells and high thermal conductivity caused by partial substitution of petroleum-based polyols by bio-based polyols. Under the same application effect, it can increase the amount of bio-based polyols added. Under the same bio-based polyol content, its application performance is better. The invention is widely applicable to industries such as home appliances and plates.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1. A multi-group modified polysiloxane, characterized by the structural formula:

wherein: m=10 to 60, n=1 to 10, r=1 to 4, p=1 to 3;

R ₁ selected from methyl, R ₂ 、R ₃ And R is ₄ Any one of them;

R ₂ has the general formula of-CH ₂ CH ₂ CH ₂ O(C ₂ H ₄ O) _a (C ₃ H ₆ O) _b R ₆ Wherein a=2 to 30, b=2 to 15, r ₆ Is H or alkyl containing 1-4 carbon atoms;

R ₃ has the general formula of-CH ₂ CH ₂ CH ₂ O(C ₂ H ₄ O) _c H, wherein c=3 to 20;

R ₄ the general formula of the catalyst is- (CH) ₂ ) _x R(CH ₂ ) _x -or- (CH) ₂ ) _x R(CH ₂ ) _x-2 CHCH ₂ X=2 to 4, wherein R has the structure: -C _w H _2w -, w=1 to 5, or

or-O (C) ₂ H ₄ O) _d (C ₃ H ₆ O) _e -，d＝0～8，e＝0～5，d+e>0 or->

t＝0～15；

R ₅ Selected from methyl, R ₂ 、R ₃ And R is ₄ Any one of the following.

2. The multi-group modified polysiloxane according to claim 1, wherein said R ₄ Is expressed as

3. A process for the preparation of a multi-radical modified polysiloxane according to any one of claims 1 to 2, comprising: the catalyst is prepared by reacting a mixture of a compound containing a carbon-carbon double bond, low-hydrogen polysiloxane, an amine auxiliary agent and a solvent under the action of a catalyst.

4. The method for producing a multi-group-modified polysiloxane according to claim 3, wherein the mass ratio of the compound having a carbon-carbon double bond, the low-hydrogen-containing polysiloxane, and the solvent is 205 to 262:50-90:40-50 parts;

preferably, the dosage of the amine auxiliary agent accounts for 80-120ppm of the total feeding amount;

preferably, the catalyst is used in a concentration of 8-12ppm in parts by weight based on the total feed;

preferably, the reaction of the mixture with the catalyst comprises: stirring the mixture in nitrogen atmosphere, heating to 85-105 ℃, preserving heat for 0.5-1h, adding the catalyst, preserving heat for 5-7h, and removing the residual solvent in the mixture.

5. The method for producing a multi-group-modified polysiloxane according to claim 4, wherein the compound having a carbon-carbon double bond comprises allyl polyether, monoallyl polyoxyethylene ether, a compound having a carbon-carbon double bond at both ends;

preferably, the mass ratio of the allyl-containing polyether, the monoallyl polyoxyethylene ether and the compound having a carbon-carbon double bond at both ends is 200 to 250:4-9:1-3.

6. The method for preparing a multi-group modified polysiloxane according to claim 5, wherein the average molecular weight of the allyl-containing polyether is 1000-1500, and the allyl-containing polyether contains 60-80 mol% of ethoxylene groups and hydroxyl groups or methyl groups are at the end.

7. The method for preparing a multi-group modified polysiloxane according to claim 5, wherein the monoallyl polyoxyethylene ether has an average molecular weight of 200 to 400;

preferably, the modifier containing carbon-carbon double bonds at both ends comprises at least one of terminal bis allyl polyether, polysiloxane containing carbon-carbon double bonds at both ends, terminal bis olefin and bisphenol A bis allyl ether;

preferably, the polysiloxane having carbon-carbon double bonds at both ends is a terminal vinyl polydimethylsiloxane.

8. The method for preparing a multi-group modified polysiloxane according to claim 3, wherein the catalyst is a palladium-containing complex, a rhodium-containing complex or a platinum-containing complex; more preferably, the catalyst is chloroplatinic acid;

preferably, the amine auxiliary comprises at least one of N, N-dimethylethanolamine, N-dibutylethanolamine, 3-dimethylpropylamine and 2-butylaminoethanol; more preferably, the amine adjuvant is NN-dimethylethanolamine;

preferably, the solvent is isopropanol or toluene.

9. Use of a multi-group modified polysiloxane according to any one of claims 1 to 2 or a multi-group modified polysiloxane prepared by a method for preparing a multi-group modified polysiloxane according to any one of claims 3 to 8 as a foam stabilizer in the preparation of polyurethane foam.

10. A polyurethane foam, characterized in that it comprises a polyether polyol, a bio-based polyol and a foam stabilizer, wherein the mass percentage of the polyether polyol and the bio-based polyol is 50-90%:10% -50%, the addition amount of the foam stabilizer is 1% -3% of the total amount of the polyether polyol and the bio-based polyol, and the foam stabilizer is the multi-group modified polysiloxane prepared by the preparation method of the multi-group modified polysiloxane according to any one of claims 1-2 or 3-8.