Polyether organic silicon copolymer containing star-shaped polyether as well as preparation method and application of polyether organic silicon copolymer

Abstract

The invention discloses a polyether organosilicon copolymer containing star-shaped polyether as well as a preparation method and application of the polyether organosilicon copolymer, and relates to the technical field of surfactants. The structural formula of the polyether organosilicon copolymer containing the star-shaped polyether is as follows: # imgabs0 #, the value of m is 30-85, p + q is equal to 5-18, and p / (p + q) is equal to 0.2-0.4; r1 is equal to-CH2CH2CH2OCH2C [CH2O (CH2CH2O) aR3] 3, a is equal to 3 to 8, and R3 is an aromatic group; r1 is-CH2CH2CH2O (CH2CH2O) x (CH2CHCH3O) yH, R2 is-CH2CH2CH2O (CH2CH2O) x (CH2CHCH3O) yH, x is 10-35, and y is 3-10. The polyether organosilicon copolymer containing the star-shaped polyether can be widely applied to preparation of foam stabilizers. The obtained rigid polyurethane foam has the characteristics of low surface defects, fine and uniform foam pores, high percentage of close area, low foam heat conductivity coefficient, high heat insulation and heat preservation capability and the like.

Description

Technical Field

[0001] The invention relates to the technical field of surfactants, and in particular to a polyether organosilicon copolymer containing star-shaped polyether, and a preparation method and application thereof. Background Art

[0002] Compared with natural insulation materials (such as rock wool, etc.) and other synthetic insulation materials (such as expanded polystyrene, etc.), rigid polyurethane foam has become the preferred material in the field of thermal insulation due to its excellent thermal insulation properties. It has a wide range of applications, including: building insulation, pipeline insulation, refrigerators, freezers, refrigerated trucks, liquefied natural gas ships and other insulation layers.

[0003] The key to the thermal insulation performance of rigid polyurethane foam lies in the foam surface and internal pore structure. The foam surface has no obvious defects and the internal pores are fine, uniform and closed, so the foam will have excellent thermal insulation performance. In the preparation process of rigid polyurethane foam, due to capillary force, the liquid in the liquid film that constitutes the bubble is transported from the bubble wall to the edge (pillar), causing the wall to thin and rupture; between two tight bubbles, there is a certain difference in size between the two bubbles, and the gas will diffuse from the smaller bubble to the larger bubble through the liquid film, causing the smaller bubble to lose and the bubble to coarsen. When two bubbles approach each other and collide, the two bubbles can merge.

[0004] At present, in order to solve the above problems, foam stabilizers are usually added to reduce foam surface defects and ensure that the internal pores are fine, uniform and closed. Foam stabilizers are usually polyether silicone surfactants with a comb-shaped structure with siloxane as the main chain and polyether as the side chain. They can emulsify the foaming raw materials to make them mix evenly, so that the foaming reaction and cross-linking reaction proceed smoothly; they can reduce the surface tension of the materials, and it is easy to make the mixed air form more bubble nuclei during stirring; however, the more important role is that during the bubble growth process, the liquid film is locally thinned, the surface area is expanded, and the surfactant concentration is reduced to produce a surface tension gradient, which prompts the surfactant to move to the thinning area and drag the lower layer of liquid to move to the thinning area, thereby restoring the liquid film thickness and preventing the bubbles from opening and rupturing; the surfactant reduces the surface tension of the bubble liquid film, and the internal pressure difference between bubbles of different sizes becomes smaller, effectively preventing the bubbles from coarsening; at the same time, the surfactants are closely arranged on the surface of the liquid film, which can not only prevent gas diffusion, but more importantly, improve the strength of the liquid film, and avoid the bubbles from being sheared and ruptured during the growth of the bubble.

[0005] Under the premise of ensuring the reduction of surface tension, when the number or molecular weight of the side chain polyether of the polyether silicone surfactant is small, the molecules are arranged closely on the surface and move quickly, which can effectively prevent the coarsening of bubbles in time and quickly reach the thinning area to avoid further thinning of the liquid film. However, the molecules carry less liquid when moving, and the liquid film cannot be repaired and is prone to rupture. At the same time, due to the small molecular weight of the surfactant, the liquid film strength is low and the shear resistance is weak, which is prone to surface defects. If the number or molecular weight of the side chain polyether is increased, the lower layer of liquid can be effectively driven to repair the thinned liquid film; at the same time, the liquid film strength is improved, the shear resistance is enhanced, and the surface defects are reduced. However, the increase in molecular weight will lead to a slower movement speed on the surface, resulting in failure to reach the area that needs to be repaired in time, resulting in bubble rupture; the number or molecular weight of the polyether will increase the area occupied by the molecules on the surface, destroying the compactness of the molecular arrangement, making gas diffusion easier, and increasing the degree of bubble coarsening.

[0006] Due to the above problems, the foams prepared by the hard polyurethane foam stabilizers prepared by the currently designed and synthesized polyether silicone surfactants have surface defects, coarse cells and open cells on the surface and inside to varying degrees, which results in the thermal conductivity of the foams being maintained at a certain level and unable to be further improved. Therefore, it is necessary to develop a polyether silicone copolymer with a new structure based on the existing structure to solve the existing problems, give full play to the role of the polyether silicone copolymer, and effectively reduce the thermal conductivity of polyurethane foam.

[0007] In view of this, the present invention is proposed. Summary of the invention

[0008] The object of the present invention is to provide a polyether organosilicon copolymer containing star-shaped polyether and a preparation method and application thereof.

[0009] The present invention is achieved in that:

[0010] In a first aspect, the present invention provides a polyether silicone copolymer containing a star-shaped polyether, the structural formula of which is as follows:

[0011]

[0012] Wherein, the value of m is 30-85, p+q=5-18 and p / (p+q)=0.2-0.4;

[0013] R1=-CH2CH2CH2OCH2C[CH2O(CH2CH2O) a R3]3, a=3-8, R3 is an aromatic group;

[0014] R2=-CH2CH2CH2O(CH2CH2O) x (CH2CHCH3O) y H, x=10-35, y=3-10.

[0015] In an optional embodiment, the structural formula of the aromatic group is as follows:

[0016]

[0017] In a second aspect, the present invention provides a method for preparing a polyether silicone copolymer containing a star-shaped polyether as described in the above embodiment, comprising:

[0018] Tribromopentaerythritol and allyl bromide are reacted to obtain allyl tribromopentaerythritol;

[0019] reacting the allyl tribromopentaerythritol with polyethylene glycol to obtain an allyl star polyether;

[0020] The allyl star polyether is reacted with a chlorinated phenyl compound to obtain a star polyether having an aromatic group at the end of the allyl group;

[0021] The polyether silicone copolymer containing the star-shaped polyether is obtained by addition reaction of hydrogen-containing polymethylsiloxane, a star-shaped polyether with an aromatic group at the end of the allyl group and an allyl polyether.

[0022] In an optional embodiment, the preparation method of allyl tribromopentaerythritol comprises: mixing tribromopentaerythritol, allyl bromide, sodium hydride and a first solvent for reaction, controlling the temperature to rise to 25-30° C., and keeping the temperature for reaction for 4-6 hours to obtain a reactant;

[0023] Preferably, the molar ratio of the tribromopentaerythritol, the allyl bromide and the sodium hydride is 1:3-5:1.5-1.8;

[0024] Preferably, the mass ratio of the total mass of the tribromopentaerythritol, the allyl bromide and the sodium hydride to the first solvent is 1:1.5-2.5;

[0025] Preferably, the first solvent is tetrahydrofuran;

[0026] Preferably, after the reaction is completed, a purification step is further included: the reactant is added dropwise to a saturated aqueous solution of ammonium chloride at a temperature of 25-30° C., stirred for 2-4 hours, allowed to stand for stratification, the organic phase is washed three times with distilled water, and then dried with anhydrous sodium sulfate, filtered to remove the solvent, and purified to obtain allyl tribromopentaerythritol.

[0027] In an alternative embodiment, the molar ratio of the allyl tribromopentaerythritol to the polyethylene glycol is 1:3.9-4.5;

[0028] Preferably, the reaction of allyl tribromopentaerythritol and polyethylene glycol comprises: first dissolving the polyethylene glycol in a second solvent, adding sodium hydride, stirring the reaction, controlling the temperature to 25-30° C., keeping the temperature for 3-5 hours, then adding the allyl tribromopentaerythritol; heating to 90-110° C., stirring the reaction for 30-60 hours, and cooling to room temperature;

[0029] Preferably, the molar ratio of the polyethylene glycol to the sodium hydride is 1:1;

[0030] Preferably, the mass ratio of the total mass of the polyethylene glycol, the sodium hydride and the allyl tribromopentaerythritol to the mass ratio of the second solvent is 1:3-6;

[0031] Preferably, the second solvent is N,N-dimethylformamide;

[0032] Preferably, after the reaction is completed, a purification step is also included:

[0033] In an alternative embodiment, the molar ratio of the allyl star polyether to the chlorophenyl compound is 1:1.3-1.5;

[0034] Preferably, the structure of the chlorophenyl compound contains only one chlorine atom connected to a benzene ring;

[0035] Preferably, the reaction of the allyl star polyether and the chlorophenyl compound comprises: adding the allyl star polyether and a catalyst into a third solvent, stirring at 40-50° C. for 1-3 hours, adding the chlorophenyl compound, raising the temperature to 80-100° C. and continuing stirring for 60-80 hours;

[0036] Preferably, the catalyst is potassium hydroxide.

[0037] Preferably, the amount of the catalyst is 0.5-2.0% of the total mass of the reaction raw materials;

[0038] Preferably, the third solvent is dimethyl sulfoxide;

[0039] Preferably, the mass ratio of the total mass of the reaction raw materials to the mass of the third solvent is 1:1-2;

[0040] Preferably, after the reaction is completed, a purification step is further included: filtering to remove the third solvent, completely dissolving the filter residue in water, extracting with chloroform, adding anhydrous sodium sulfate to dry, filtering, and purifying to obtain a star-shaped polyether with an aromatic group at the end of the allyl group.

[0041] In an optional embodiment, the molar ratio of the sum of the allyl double bonds in the star-shaped polyether having an aromatic group at the end of the allyl group and the allyl polyether to the silicon-hydrogen bonds in the hydrogen-containing polymethylsiloxane is 1.2-1.6:1;

[0042] Preferably, the addition reaction comprises: adding the hydrogen-containing polymethylsiloxane, the star-shaped polyether having an aromatic group at the end of the allyl group and the fourth solvent into a reactor, heating to 90-100° C. at normal pressure for reaction for 1 hour in the presence of a chloroplatinic acid catalyst and a co-catalyst; continuing to add the allyl polyether and the chloroplatinic acid catalyst, heating to 100-120° C. at normal pressure for reaction for 5-10 hours, and removing the solvent under reduced pressure to obtain a polyether organosilicon copolymer containing a star-shaped polyether;

[0043] Preferably, the fourth solvent is toluene;

[0044] Preferably, the mass ratio of the fourth solvent to the total mass of the reaction raw materials is 1:0.5-1.

[0045] In a third aspect, the present invention provides a polyether silicone copolymer containing a star-shaped polyether as described in any one of the aforementioned embodiments or a polyether silicone copolymer containing a star-shaped polyether prepared by the preparation method of a polyether silicone copolymer containing a star-shaped polyether as described in any one of the aforementioned embodiments in the preparation of a foam stabilizer.

[0046] In a fourth aspect, the present invention provides a foam stabilizer, comprising a polyether silicone copolymer containing a star-shaped polyether as described in any one of the aforementioned embodiments or a polyether silicone copolymer containing a star-shaped polyether prepared by the method for preparing a polyether silicone copolymer containing a star-shaped polyether as described in any one of the aforementioned embodiments.

[0047] In a fifth aspect, the present invention provides a rigid polyurethane foam, the components of which include the foam stabilizer as described in the above embodiment.

[0048] The present invention has the following beneficial effects:

[0049] The polyether organosilicon copolymer containing star-shaped polyether provided by the present invention is prepared by grafting star-shaped polyether and allyl polyether with aromatic groups at the end of allyl groups on the main chain of hydrogen-containing polymethylsiloxane, and limiting the amount of R1 group and R2 group to p / (p+q)=0.2-0.4. The polyether organosilicon copolymer containing star-shaped polyether partially replaces the linear polyether with the star-shaped polyether, and the migration ability of the copolymer on the surface of the liquid film is increased. The star-shaped polyether mainly drags the liquid material in the shallow layer under the liquid film, and the ability of the copolymer to repair the thinning area is significantly enhanced, thereby reducing the rupture of bubbles. Meanwhile, compared with the organosilicon copolymer with the linear polyether as the side chain, the organosilicon copolymer containing star-shaped polyether overcomes the problem of coarsening of bubbles caused by the decrease in the compactness of the copolymer surface arrangement due to the large molecular weight of the linear polyether because each of its side chains is shorter. The linear chain of the star-shaped polyether is fully combined with the liquid in the shallow layer under the liquid film to effectively improve the surface strength of the liquid surface, significantly enhance the shear resistance, and thus reduce surface defects. At the same time, aromatic groups are introduced at the ends of the star-shaped polyether to improve the emulsification ability of the reaction materials (isocyanate, polyol, foaming agent, etc.) during the preparation of the polyurethane foam, ensuring that the foaming reaction and the cross-linking reaction are carried out efficiently. The design and synthesis of the polyether silicone copolymer containing the star-shaped polyether effectively solves the problem that conventional polyether silicone copolymers cannot simultaneously reduce surface defects, open pores and coarsening, which makes it difficult to further reduce the thermal conductivity, significantly improves the quality of polyurethane foam, and prepares a rigid polyurethane foam with low surface defects, fine and uniform pores, and a high closed cell rate, which greatly reduces the thermal conductivity of the foam and improves the thermal insulation capacity of the foam. The preparation method of the polyether silicone copolymer containing star-shaped polyether provided by the present invention first prepares allyl tribromopentaerythritol; then, reacts with polyethylene glycol to obtain allyl star-shaped polyether; then, reacts with a chlorophenyl compound to obtain a star-shaped polyether with an aromatic group at the end of the allyl group; finally, the star-shaped polyether with an aromatic group at the end of the allyl group and the allyl polyether are grafted on the main chain of hydrogen-containing polymethylsiloxane to synthesize the polyether silicone copolymer containing star-shaped polyether. The whole synthesis process is simple to operate and easy to implement, and the preparation of the star-shaped polyether with an aromatic group at the end of the allyl group can be gradually realized, and the grafting ratio between the star-shaped polyether with an aromatic group at the end of the allyl group and the allyl polyether can also be limited, so as to prepare a polyether silicone copolymer containing star-shaped polyether that meets the requirements. The polyether silicone copolymer containing star-shaped polyether can be widely used in the preparation of foam stabilizers. The rigid polyurethane foam prepared by using the method has the characteristics of low surface defects, fine and uniform pores, high closed cell rate, low foam thermal conductivity, high thermal insulation capacity, etc., which can significantly improve the quality of polyurethane foam. DETAILED DESCRIPTION

[0050] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0051] The present invention provides a polyether organosilicon copolymer containing a star-shaped polyether, and the structural formula thereof is as follows:

[0052]

[0053] Wherein, the value of m is 30-85, p+q=5-18 and p / (p+q)=0.2-0.4;

[0054] R1=-CH2CH2CH2OCH2C[CH2O(CH2CH2O) a R3]3, a=3-8, R3 is an aromatic group;

[0055] R2=-CH2CH2CH2O(CH2CH2O) x (CH2CHCH3O) y H, x=10-35, y=3-10.

[0056] In the present invention, a polyether silicone copolymer containing a star polyether is synthesized by grafting a star polyether and an allyl polyether with an aromatic group at the end of the allyl group on the main chain of a hydrogen-containing polymethylsiloxane, and the amount of the R1 group and the R2 group is limited to p / (p+q)=0.2-0.4. In the present invention, the star polyether is used to partially replace the linear polyether, and the migration ability of the copolymer on the surface of the liquid film is increased. The star polyether mainly drags the liquid material in the shallow layer under the liquid film, and its ability to repair the thinning area is significantly enhanced, reducing bubble rupture; at the same time, compared with the silicone copolymer with a linear polyether as the side chain, the silicone copolymer containing a star polyether has a shorter side chain and a flexible and changeable conformation, which overcomes the problem of bubble coarsening caused by the decrease in the compactness of the copolymer surface arrangement due to the large molecular weight of the linear polyether; the linear chain of the star polyether is fully combined with the liquid in the shallow layer under the liquid film to effectively improve the surface strength of the liquid surface, significantly enhance the shear resistance, and thus reduce surface defects. At the same time, aromatic groups are introduced at the ends of the star-shaped polyether to improve the emulsification ability of the reaction materials (isocyanate, polyol, foaming agent, etc.) during the preparation of the polyurethane foam, ensuring the efficient foaming reaction and cross-linking reaction. The design and synthesis of the polyether silicone copolymer containing the star-shaped polyether effectively solves the problem that conventional polyether silicone copolymers cannot simultaneously reduce surface defects, open pores and coarsening, which makes it difficult to further reduce the thermal conductivity, significantly improves the quality of polyurethane foam, and prepares rigid polyurethane foam with low surface defects, fine and uniform pores, and high closed cell rate, which greatly reduces the thermal conductivity of the foam and improves the thermal insulation capacity of the foam.

[0057] Among them, the structural formula of the aromatic group is as follows:

[0058]

[0059] The present invention provides a method for preparing a polyether organosilicon copolymer containing a star-shaped polyether, which comprises the following steps:

[0060] S1. Tribromopentaerythritol (C(CH2Br)3CH2OH) and allyl bromide (CH2=CH-CH2Br) are reacted to obtain allyl tribromopentaerythritol (CH2=CH-CH2OC(CH2Br)3).

[0061] Under argon protection, the temperature is controlled at 0-5°C, tribromopentaerythritol, allyl bromide, sodium hydride and the first solvent are mixed for reaction, the temperature is controlled to rise to 25-30°C, and the reaction is kept warm for 4-6 hours to obtain a reactant; the reactant is added dropwise to a saturated aqueous solution of ammonium chloride at a temperature of 25-30°C, stirred for 2-4 hours, allowed to stand for stratification, the organic phase is washed with distilled water for 3 times, then dried with anhydrous sodium sulfate, filtered to remove the solvent, and purified to obtain allyl tribromopentaerythritol.

[0062] The molar ratio of tribromopentaerythritol, allyl bromide and sodium hydride is 1:3-5:1.5-1.8; the mass ratio of the total mass of tribromopentaerythritol, allyl bromide and sodium hydride to the first solvent is 1:1.5-2.5; and the first solvent is tetrahydrofuran.

[0063] S2, allyl tribromopentaerythritol and polyethylene glycol (HO-(CH2CH2O) a -H) reaction to obtain allyl star polyether (CH2=CHCH2OCH2C[CH2O(CH2CH2O) a H]3.

[0064] Under argon protection, control the temperature at 0-5°C, first dissolve polyethylene glycol in the second solvent, add sodium hydride, stir the reaction, control the temperature to 25-30°C, keep the temperature for 3-5h, then add allyl tribromopentaerythritol; heat to 90-110°C, stir the reaction for 30-60h, cool to room temperature; add distilled water, stir, stand and separate; extract the aqueous phase with dichloromethane, add anhydrous sodium sulfate to dry, filter and remove the solvent, purify and vacuum dry to obtain allyl star polyether.

[0065] The molar ratio of allyl tribromopentaerythritol to polyethylene glycol is 1:3.9-4.5; the molar ratio of polyethylene glycol to sodium hydride is 1:1; the mass ratio of the total mass of polyethylene glycol, sodium hydride and allyl tribromopentaerythritol to the mass ratio of the second solvent is 1:3-6; and the second solvent is N,N-dimethylformamide.

[0066] S3, reacting the allyl star polyether with a chlorinated phenyl compound to obtain a star polyether having an aromatic group at the end of the allyl group (CH2=CHCH2OCH2C[CH2O(CH2CH2O) a R3]3.

[0067] Add allyl star polyether and catalyst into the third solvent, stir at 40-50°C for 1-3h, add chlorophenyl compound, raise the temperature to 80-100°C and continue stirring for 60-80h; filter to remove the third solvent, completely dissolve the filter residue in water, extract with chloroform, add anhydrous sodium sulfate to dry, filter, and purify to obtain star polyether with aromatic group at the end of allyl group.

[0068] The molar ratio of allyl star polyether to chlorophenyl compound is 1:1.3-1.5; the amount of catalyst used is 0.5-2.0% of the total mass of the reaction raw materials; the total mass ratio of allyl star polyether and chlorophenyl compound to the third solvent is 1:1-2; the catalyst is potassium hydroxide, and the third solvent is dimethyl sulfoxide.

[0069] In this embodiment, the structure of the chlorophenyl compound contains only one chlorine atom connected to a benzene ring, and the chlorophenyl compound includes but is not limited to 2-chlorophenethyl ether, 4-tert-butylchlorobenzene, and 5-chlorobenzofuran.

[0070] The chlorine atom in the chlorophenyl compound reacts with the H in the allyl star polyether, thereby introducing the aromatic group in the chlorophenyl compound into the terminal of the allyl group to form a star polyether with an aromatic group at the terminal of the allyl group. The introduction of the aromatic group at the terminal of the star polyether can improve the emulsification ability of the reaction materials (isocyanate, polyol, foaming agent, etc.) during the preparation of the polyurethane foam, and ensure the efficient foaming reaction and cross-linking reaction.

[0071] S4, hydrogen-containing polymethylsiloxane ((CH3)3SiO-[Si(CH3)2O] m -[SiH(CH3)O] p+q -Si(CH3)3), star-shaped polyethers with aromatic groups at the end of the allyl groups and allyl polyethers (CH2=CHCH2O(CH2CH2O) x (CH2CHCH3O) y H) performing an addition reaction to obtain a polyether organosilicon copolymer containing a star-shaped polyether.

[0072] Add hydrogen-containing polymethylsiloxane, star-shaped polyether with aromatic groups at the end of allyl group and fourth solvent into the reactor, heat to 90-100° C. at normal pressure for reaction for 1 hour in the presence of chloroplatinic acid catalyst and co-catalyst; continue to add allyl polyether and chloroplatinic acid catalyst, heat to 100-120° C. at normal pressure for reaction for 5-10 hours, remove the solvent under reduced pressure, and obtain a polyether organosilicon copolymer containing star-shaped polyether;

[0073] Among them, the molar ratio of the sum of allyl double bonds in the star-shaped polyether with aromatic groups at the allyl end and the allyl polyether to the silicon-hydrogen bonds in the hydrogen-containing polymethylsiloxane is 1.2-1.6:1; the fourth solvent is toluene; the mass ratio of the total mass of the hydrogen-containing polymethylsiloxane, the star-shaped polyether with aromatic groups at the allyl end, and the allyl polyether to the fourth solvent is 1:0.5-1.

[0074] The polyether silicone copolymer containing the star-shaped polyether can be widely used in the preparation of foam stabilizers.

[0075] Correspondingly, the present invention also provides a foam stabilizer, which includes the above-mentioned polyether silicone copolymer containing star-shaped polyether.

[0076] In addition, the present invention provides a rigid polyurethane foam, the components of which include the above foam stabilizer. Based on 100 parts by mass pphp of polyether polyol or polyester polyol, the mass fraction of the polyether silicone copolymer is 1-5 pphp, preferably 2-3 pphp.

[0077] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0078] Example 1

[0079] The present invention provides a polyether organosilicon copolymer containing a star-shaped polyether, and a preparation method thereof comprises the following steps:

[0080] (1) Preparation of allyl tribromopentaerythritol

[0081] Under argon protection, control the temperature at 0°C, mix 37.90g tribromopentaerythritol and 62.10g allyl bromide with 200.00g tetrahydrofuran, and after mixing evenly, add 4.34g sodium hydride, stir to react, control the temperature to 25°C, and keep the temperature for 6h. Then add the reactant dropwise to a saturated aqueous solution of ammonium chloride, keep the temperature at 25°C, stir for 3h, and stand for stratification. Take the organic phase, wash it with distilled water 3 times, add anhydrous sodium sulfate to dry, filter and remove the solvent, and purify to obtain allyl tribromopentaerythritol.

[0082] (2) Preparation of allyl star polyether

[0083] Under argon protection, control the temperature at 3°C, dissolve 67.48g of polyethylene glycol in 400g of N,N-dimethylformamide, add 8.35g of sodium hydride, stir to react, control the temperature to 25°C, and keep the temperature for 3h; then add 32.52g of allyl tribromopentaerythritol, heat to 90°C, stir to react for 50h, and cool to room temperature; add distilled water, stir, and stand to separate; extract the aqueous phase with dichloromethane, add anhydrous sodium sulfate to dry, filter to remove the solvent, purify and vacuum dry to obtain allyl star polyether.

[0084] (3) Preparation of star-shaped polyethers with aromatic groups at the end of allyl groups

[0085] 51.70 g of allyl star polyether and 2.00 g of potassium hydroxide were added to 150.00 g of dimethyl sulfoxide, stirred at 45°C for 3 h, and 48.30 g of 2-chlorophenyl ether was added, and the temperature was raised to 95°C and stirred for 70 h. The solvent was removed, and the mixture was completely dissolved in water, extracted with chloroform, dried with anhydrous sodium sulfate, filtered, and the solvent was removed. After purification, a star polyether containing allyl groups and aromatic groups at the end was obtained.

[0086] (4) Preparation of polyether silicone copolymers containing star-shaped polyethers

[0087] 36.56g of hydrogen-containing polymethylsiloxane, 13.55g of star-shaped polyether, and 80.00g of toluene were added to the reactor, and heated to 95°C at normal pressure for 1h in the presence of 3ppm chloroplatinic acid catalyst and 75ppm triethanolamine as a co-catalyst; 49.88g of allyl polyether and 12ppm chloroplatinic acid catalyst were added, and the temperature was heated to 115°C for 6.0h, and the solvent was removed under reduced pressure to obtain a polyether silicone copolymer containing star-shaped polyether. Its structural characterization is as follows:

[0088] (CH3)3Si-O-[Si(CH3)2O] 51 -[Si(CH3)R1O] 1.5 -[Si(CH3)R2O] 5.5 -Si(CH3)3;

[0089] in:

[0090] R1=-CH2CH2CH2OCH2C[CH2O(CH2CH2O)4R3]3;

[0091] R2=-CH2CH2CH2O(CH2CH2O) 11 (CH2CHCH3O)3H;

[0092]

[0093] Example 2

[0094] The present invention provides a polyether organosilicon copolymer containing a star-shaped polyether, and a preparation method thereof comprises the following steps:

[0095] (1) Preparation of allyl tribromopentaerythritol

[0096] Under argon protection, control the temperature at 5°C, mix 43.42g of tribromopentaerythritol and 56.58g of allyl bromide with 180.00g of tetrahydrofuran, and after mixing evenly, add 5.13g of sodium hydride, stir to react, control the temperature to 30°C, and keep the temperature for 4h. Then add the reactant dropwise to a saturated aqueous solution of ammonium chloride, keep the temperature at 30°C, stir for 2h, and stand for stratification. Take the organic phase, wash it with distilled water 3 times, add anhydrous sodium sulfate to dry, filter and remove the solvent, and purify to obtain allyl tribromopentaerythritol.

[0097] (2) Preparation of allyl star polyether

[0098] Under argon protection, control the temperature at 5°C, dissolve 77.68g of polyethylene glycol in 350g of N,N-dimethylformamide, add 6.61g of sodium hydride, stir to react, control the temperature to 30°C, and keep the temperature for 4h; add 22.32g of allyl tribromopentaerythritol, heat to 100°C, stir to react for 35h, and cool to room temperature; add distilled water, stir, stand and separate; extract the aqueous phase with dichloromethane, add anhydrous sodium sulfate to dry, filter to remove the solvent, purify and vacuum dry to obtain allyl star polyether.

[0099] (3) Preparation of star-shaped polyethers with aromatic groups at the end of allyl groups

[0100] 59.54 g of allyl-containing star-shaped polyether and 1.50 g of potassium hydroxide were added to 200.00 g of dimethyl sulfoxide, stirred at 50° C. for 2 h, and 40.46 g of 4-tert-butyl chlorobenzene was added, and the temperature was raised to 85° C. and stirred for 76 h. The solvent was removed, and the mixture was completely dissolved in water, extracted with chloroform, dried with anhydrous sodium sulfate, filtered, and the solvent was removed. After purification, a star-shaped polyether with an aromatic group at the end of the allyl group was obtained.

[0101] (4) Preparation of polyether silicone copolymers containing star-shaped polyethers

[0102] 37.82g hydrogen-containing polymethylsiloxane, 15.55g star-shaped polyether, and 50.00g toluene were added to the reactor, and heated to 95°C under normal pressure for 1h in the presence of 3ppm chloroplatinic acid catalyst and 60ppm triethylamine co-catalyst; 46.63g allyl polyether and 12ppm chloroplatinic acid catalyst were added, and heated to 105°C for 5.0h, and the solvent was removed under reduced pressure to obtain a polyether silicone copolymer containing star-shaped polyether. Its structural characterization is as follows:

[0103] (CH3)3Si-O-[Si(CH3)2O] 39 -[Si(CH3)R1O]1-[Si(CH3)R2O]4-Si(CH3)3;

[0104] in:

[0105] R1=-CH2CH2CH2OCH2C[CH2O(CH2CH2O)6R3]3;

[0106] R2=-CH2CH2CH2O(CH2CH2O) 13 (CH2CHCH3O)1H;

[0107]

[0108] Example 3

[0109] The present invention provides a polyether organosilicon copolymer containing a star-shaped polyether, and a preparation method thereof comprises the following steps:

[0110] (1) Preparation of allyl tribromopentaerythritol

[0111] Under argon protection, control the temperature at 0°C, mix 47.24g tribromopentaerythritol and 52.67g allyl bromide with 200.00g tetrahydrofuran, and after mixing evenly, add 6.11g sodium hydride, stir to react, control the temperature to 25°C, and keep the temperature for 5h. Then add the reactant dropwise to a saturated aqueous solution of ammonium chloride, keep the temperature at 25°C, stir for 4h, and stand for stratification. Take the organic phase, wash it with distilled water 3 times, add anhydrous sodium sulfate to dry, filter and remove the solvent, and purify to obtain allyl tribromopentaerythritol.

[0112] (2) Preparation of allyl star polyether

[0113] Under argon protection, control the temperature at 0°C, dissolve 71.79g of polyethylene glycol in 300g of N,N-dimethylformamide, add 7.24g of sodium hydride, stir to react, control the temperature to 25°C, and keep the temperature for 5h; add 28.21g of allyl tribromopentaerythritol, heat to 95°C, stir to react for 45h, and cool to room temperature; add distilled water, stir, stand and separate; extract the aqueous phase with dichloromethane, add anhydrous sodium sulfate to dry, filter and remove the solvent, purify and vacuum dry to obtain allyl star polyether.

[0114] (3) Preparation of star-shaped polyethers with aromatic groups at the end of allyl groups

[0115] 54.90g of allyl-containing star-shaped polyether and 1.80g of potassium hydroxide were added to 180.00g of dimethyl sulfoxide, stirred at 40°C for 2.5h, and 45.10g of 5-chlorobenzofuran was added, and the temperature was raised to 100°C and stirred for 65h. The solvent was removed, and the mixture was completely dissolved in water, extracted with chloroform, dried with anhydrous sodium sulfate, filtered, and the solvent was removed. After purification, a star-shaped polyether with an aromatic group at the end of the allyl group was obtained.

[0116] (4) Preparation of polyether silicone copolymers containing star-shaped polyethers

[0117] 25.58g hydrogen-containing polymethylsiloxane, 14.46g star-shaped polyether, and 60.00g toluene were added to the reactor, and heated to 90°C at normal pressure for 1h in the presence of 4ppm chloroplatinic acid catalyst and 50ppm N,N-dimethylaniline as a co-catalyst; 59.96g allyl polyether and 15ppm chloroplatinic acid catalyst were added, and the temperature was heated to 105°C for 5.0h, and the solvent was removed under reduced pressure to obtain a polyether silicone copolymer containing star-shaped polyether. Its structural characterization is as follows:

[0118] (CH3)3Si-O-[Si(CH3)2O] 62 -[Si(CH3)R1O] 2.5 -[Si(CH3)R2O] 6.5 -Si(CH3)3;

[0119] in:

[0120] R1=-CH2CH2CH2OCH2C[CH2O(CH2CH2O)5R3]3;

[0121] R2=-CH2CH2CH2O(CH2CH2O) 20 (CH2CHCH3O)5H;

[0122]

[0123] Example 4

[0124] The present invention provides a polyether organosilicon copolymer containing a star-shaped polyether, and a preparation method thereof comprises the following steps:

[0125] (1) Preparation of allyl tribromopentaerythritol

[0126] Under argon protection, control the temperature at 5°C, mix 43.42g of tribromopentaerythritol and 56.58g of allyl bromide with 180.00g of tetrahydrofuran, and after mixing evenly, add 5.13g of sodium hydride, stir to react, control the temperature to 30°C, and keep the temperature for 4h. Then add the reactant dropwise to a saturated aqueous solution of ammonium chloride, keep the temperature at 30°C, stir for 2h, and stand for stratification. Take the organic phase, wash it with distilled water 3 times, add anhydrous sodium sulfate to dry, filter and remove the solvent, and purify to obtain allyl tribromopentaerythritol.

[0127] (2) Preparation of allyl star polyether

[0128] Under argon protection, the temperature was controlled at 5°C, 77.68g of polyethylene glycol was dissolved in 350g of N,N-dimethylformamide, 6.61g of sodium hydride was added, the reaction was stirred, the temperature was controlled to rise to 30°C, and the reaction was kept warm for 4h; 22.32g of allyl tribromopentaerythritol was added, the mixture was heated to 100°C, the reaction was stirred for 35h, and the mixture was cooled to room temperature; distilled water was added, stirred, and allowed to stand for stratification; the aqueous phase was extracted with dichloromethane, dried with anhydrous sodium sulfate, filtered to remove the solvent, and purified and vacuum dried to obtain an allyl-containing star polyether.

[0129] (3) Preparation of star-shaped polyethers with aromatic groups at the end of allyl groups

[0130] 60.16 g of allyl-containing star-shaped polyether and 1.30 g of potassium hydroxide were added to 190.00 g of dimethyl sulfoxide, stirred at 47°C for 2 h, and 39.84 g of 5-chlorobenzofuran was added, and the temperature was raised to 98°C and stirred for 60 h. The solvent was removed, and the mixture was completely dissolved in water, extracted with chloroform, dried with anhydrous sodium sulfate, filtered, and the solvent was removed. After purification, a star-shaped polyether with an aromatic group at the end of the allyl group was obtained.

[0131] (4) Preparation of polyether silicone copolymers containing star-shaped polyethers

[0132] 26.10g hydrogen-containing polymethylsiloxane, 22.93g star-shaped polyether, and 90.00g toluene were added to the reactor, and heated to 90°C at normal pressure for 1h in the presence of 4ppm chloroplatinic acid catalyst and 80ppm triethanolamine catalyst; 50.97g allyl polyether and 18ppm chloroplatinic acid catalyst were added, and the temperature was heated to 115°C for 8.0h, and the solvent was removed under reduced pressure to obtain a polyether silicone copolymer containing star-shaped polyether. Its structural characterization is as follows:

[0133] (CH3)3Si-O-[Si(CH3)2O] 80 -[Si(CH3)R1O] 4.5 -[Si(CH3)R2O] 7.5 -Si(CH3)3;

[0134] in:

[0135] R1=-CH2CH2CH2OCH2C[CH2O(CH2CH2O)6R3]3;

[0136] R2=-CH2CH2CH2O(CH2CH2O) 14 (CH2CHCH3O)7H;

[0137]

[0138] Example 5

[0139] The present invention provides a polyether organosilicon copolymer containing a star-shaped polyether, and a preparation method thereof comprises the following steps:

[0140] (1) Preparation of allyl tribromopentaerythritol

[0141] Under argon protection, control the temperature at 0°C, mix 47.24g tribromopentaerythritol and 52.67g allyl bromide with 200.00g tetrahydrofuran, and after mixing evenly, add 6.11g sodium hydride, stir to react, control the temperature to 25°C, and keep the temperature for 5h. Then add the reactant dropwise to a saturated aqueous solution of ammonium chloride, keep the temperature at 25°C, stir for 4h, and stand for stratification. Take the organic phase, wash it with distilled water 3 times, add anhydrous sodium sulfate to dry, filter and remove the solvent, and purify to obtain allyl tribromopentaerythritol.

[0142] (2) Preparation of allyl star polyether

[0143] Under argon protection, control the temperature at 0°C, dissolve 71.79g of polyethylene glycol in 300g of N,N-dimethylformamide, add 7.24g of sodium hydride, stir to react, control the temperature to 25°C, and keep the temperature for 5h; add 28.21g of allyl tribromopentaerythritol, heat to 95°C, stir to react for 45h, and cool to room temperature; add distilled water, stir, stand and separate; extract the aqueous phase with dichloromethane, add anhydrous sodium sulfate to dry, filter and remove the solvent, purify and vacuum dry to obtain the allyl-containing star polyether.

[0144] (3) Preparation of star-shaped polyethers with aromatic groups at the end of allyl groups

[0145] 54.26g of allyl-containing star-shaped polyether and 2.00g of potassium hydroxide were added to 180.00g of dimethyl sulfoxide, stirred at 45°C for 2.5h, and 45.74g of 2-chlorophenyl ether was added, and the temperature was raised to 80°C and stirred for 80h. The solvent was removed, and the mixture was completely dissolved in water, extracted with chloroform, dried with anhydrous sodium sulfate, filtered, and the solvent was removed. After purification, a star-shaped polyether containing an allyl terminal aromatic group was obtained.

[0146] (4) Preparation of polyether silicone copolymers containing star-shaped polyethers

[0147] 28.32g of hydrogen-containing polymethylsiloxane, 16.07g of star-shaped polyether, and 50.00g of toluene were added to the reactor, and heated to 95°C at normal pressure for 1h in the presence of 5ppm chloroplatinic acid catalyst and 70ppm triethylamine catalyst; 55.61g of allyl polyether and 18ppm chloroplatinic acid catalyst were added, and the temperature was heated to 110°C for 6h, and the solvent was removed under reduced pressure to obtain a polyether silicone copolymer containing star-shaped polyether. Its structural characterization is as follows:

[0148] (CH3)3Si-O-[Si(CH3)2O] 76 -[Si(CH3)R1O]3-[Si(CH3)R2O]7-Si(CH3)3;

[0149] in:

[0150] R1=-CH2CH2CH2OCH2C[CH2O(CH2CH2O)5R3]3;

[0151] R2=-CH2CH2CH2O(CH2CH2O) 18 (CH2CHCH3O)5H;

[0152]

[0153] Example 6

[0154] The present invention provides a polyether organosilicon copolymer containing a star-shaped polyether, and a preparation method thereof comprises the following steps:

[0155] (1) Preparation of allyl tribromopentaerythritol

[0156] Under argon protection, control the temperature at 0°C, mix 37.90g tribromopentaerythritol and 62.10g allyl bromide with 200.00g tetrahydrofuran, and after mixing evenly, add 4.34g sodium hydride, stir to react, control the temperature to 25°C, and keep the temperature for 6h. Then add the reactant dropwise to a saturated aqueous solution of ammonium chloride, keep the temperature at 25°C, stir for 3h, and stand for stratification. Take the organic phase, wash it with distilled water 3 times, add anhydrous sodium sulfate to dry, filter and remove the solvent, and purify to obtain allyl tribromopentaerythritol.

[0157] (2) Preparation of allyl star polyether

[0158] Under argon protection, the temperature was controlled at 3°C, 67.48g of polyethylene glycol was dissolved in 400g of N,N-dimethylformamide, 8.35g of sodium hydride was added, the reaction was stirred, the temperature was controlled to rise to 25°C, and the reaction was kept warm for 3h; then 32.52g of allyl tribromopentaerythritol was added, the mixture was heated to 90°C, the reaction was stirred for 50h, and the mixture was cooled to room temperature; distilled water was added, stirred, and allowed to stand for stratification; the aqueous phase was extracted with dichloromethane, dried with anhydrous sodium sulfate, filtered to remove the solvent, and purified and vacuum dried to obtain an allyl-containing star polyether.

[0159] (3) Preparation of star-shaped polyethers with aromatic groups at the end of allyl groups

[0160] 51.69g of allyl-containing star-shaped polyether and 1.10g of potassium hydroxide were added to 200.00g of dimethyl sulfoxide, stirred at 50°C for 3.0h, and 48.31g of 4-tert-butyl chlorobenzene was added, and the temperature was raised to 95°C and stirred for 73h. The solvent was removed, and the mixture was completely dissolved in water, extracted with chloroform, dried with anhydrous sodium sulfate, filtered, and the solvent was removed. After purification, a star-shaped polyether containing allyl groups and having aromatic groups at the end was obtained.

[0161] (4) Preparation of polyether silicone copolymers containing star-shaped polyethers

[0162] 36.30g hydrogen-containing polymethylsiloxane, 22.17g star-shaped polyether, and 60.00g toluene were added to the reactor, and heated to 90°C at normal pressure for 1h in the presence of 5ppm chloroplatinic acid catalyst and 40ppm N,N-dimethylaniline catalyst; 41.54g allyl polyether and 16ppm chloroplatinic acid catalyst were added, and the temperature was heated to 110°C for 6h, and the solvent was removed under reduced pressure to obtain a polyether silicone copolymer containing star-shaped polyether. Its structural characterization is as follows:

[0163] (CH3)3Si-O-[Si(CH3)2O] 43 -[Si(CH3)R1O]2-[Si(CH3)R2O]3-Si(CH3)3;

[0164] in:

[0165] R1=-CH2CH2CH2OCH2C[CH2O(CH2CH2O)4R3]3;

[0166] R2=-CH2CH2CH2O(CH2CH2O) 15 (CH2CHCH3O)2H;

[0167]

[0168] Comparative Example 1

[0169] This comparative example provides a polyether silicone copolymer, and its preparation method comprises:

[0170] 38.3 g of hydrogen-containing polymethylsiloxane, 61.7 g of allyl polyether and 80.00 g of toluene from step (4) of Example 1 were added to a reactor, heated to 115° C. for 6.0 h in the presence of 12 ppm of chloroplatinic acid catalyst and 75 ppm of triethanolamine as a co-catalyst, and the solvent was removed under reduced pressure to obtain a polyether silicone copolymer free of star-shaped polyether. Its structural characteristics are as follows:

[0171] (CH3)3Si-O-[Si(CH3)2O] 51 -[Si(CH3)R2O]7-Si(CH3)3;

[0172] in:

[0173] R2=-CH2CH2CH2O(CH2CH2O) 11 (CH2CHCH3O)3H;

[0174] Comparative Example 2

[0175] (1) Preparation of allyl tribromopentaerythritol

[0176] Allyl tribromopentaerythritol was prepared according to step (1) in Example 2.

[0177] (2) Preparation of allyl star polyether

[0178] According to step (2) in Example 2, allyl star polyether was prepared.

[0179] (3) Preparation of polyether silicone copolymers containing star-shaped polyethers

[0180] 39.65 g of hydrogenated polymethylsiloxane from step (4) of Example 2, 11.46 g of star-shaped polyether prepared in step (2) above, and 50.00 g of toluene were added to the reactor, and heated to 95° C. at normal pressure for 1 h in the presence of 3 ppm chloroplatinic acid catalyst and 60 ppm triethylamine as a co-catalyst; 48.89 g of allyl polyether and 12 ppm chloroplatinic acid catalyst were added, and the temperature was heated to 105° C. for 5.0 h, and the solvent was removed under reduced pressure to obtain a polyether organosilicon copolymer containing star-shaped polyether. Its structural characterization is as follows:

[0181] (CH3)3Si-O-[Si(CH3)2O] 39 -[Si(CH3)R1O]1-[Si(CH3)R2O]4-Si(CH3)3;

[0182] in:

[0183] R1=-CH2CH2CH2OCH2C[CH2O(CH2CH2O)6H]3;

[0184] R2=-CH2CH2CH2O(CH2CH2O) 13 (CH2CHCH3O)1H;

[0185] Comparative Example 3

[0186] (1) Preparation of allyl tribromopentaerythritol

[0187] Allyl tribromopentaerythritol was prepared according to step (1) in Example 3.

[0188] (2) Preparation of allyl star polyether

[0189] According to step (2) in Example 3, allyl star polyether was prepared.

[0190] (3) Preparation of star-shaped polyethers with aromatic groups at the end of allyl groups

[0191] According to step (3) in Example 3, a star-shaped polyether having an aromatic group at the end of the allyl group was prepared.

[0192] (4) Preparation of polyether silicone copolymers containing star-shaped polyethers

[0193] 25.65g of hydrogen-containing polymethylsiloxane from step (4) of Example 3, 26.11g of star-shaped polyether prepared in step (3) above, and 60.00g of toluene were added to the reactor, and heated to 90°C at normal pressure for 1h in the presence of 4ppm chloroplatinic acid catalyst and 50ppm N,N-dimethylaniline as a co-catalyst; 48.24g of allyl polyether from step (4) of Example 3 and 15ppm chloroplatinic acid catalyst were added, and the temperature was heated to 105°C for 5.0h, and the solvent was removed under reduced pressure to obtain a polyether silicone copolymer containing a star-shaped polyether. Its structural characterization is as follows:

[0194] (CH3)3Si-O-[Si(CH3)2O] 62 -[Si(CH3)R1O] 4.5 -[Si(CH3)R2O] 4.5 -Si(CH3)3;

[0195] in:

[0196] R1=-CH2CH2CH2OCH2C[CH2O(CH2CH2O)5R3]3;

[0197] R2=-CH2CH2CH2O(CH2CH2O) 20 (CH2CHCH3O)5H;

[0198]

[0199] Comparative Example 4

[0200] (1) Preparation of polyether silicone copolymer

[0201] 27.27 g of hydrogen-containing polymethylsiloxane, 72.73 g of allyl polyether and 90.00 g of toluene from step (4) of Example 4 were added to a reactor, heated to 115° C. for 8.0 h in the presence of 18 ppm chloroplatinic acid catalyst and 80 ppm triethanolamine catalyst, and the solvent was removed under reduced pressure to obtain a polyether silicone copolymer. Its structural characteristics are as follows:

[0202] (CH3)3Si-O-[Si(CH3)2O] 80 -[Si(CH3)R2O] 12 -Si(CH3)3;

[0203] in:

[0204] R2=-CH2CH2CH2O(CH2CH2O) 14 (CH2CHCH3O)7H.

[0205] Comparative Example 5

[0206] (1) Preparation of allyl tribromopentaerythritol

[0207] Allyl tribromopentaerythritol was prepared according to step (1) in Example 5.

[0208] (2) Preparation of allyl star polyether

[0209] According to step (2) in Example 5, allyl star polyether was prepared.

[0210] (3) Preparation of polyether silicone copolymers containing star-shaped polyethers

[0211] 29.79g of hydrogen-containing polymethylsiloxane in step (4) of Example 5, 11.70g of star-shaped polyether prepared in step (2) above, and 50.00g of toluene were added to the reactor, and heated to 95°C at normal pressure for 1h in the presence of 5ppm chloroplatinic acid catalyst and 70ppm triethylamine catalyst; 58.51g of allyl polyether and 18ppm chloroplatinic acid catalyst were added, and the temperature was heated to 110°C for 6.0h, and the solvent was removed under reduced pressure to obtain a polyether silicone copolymer containing star-shaped polyether. Its structural characterization is as follows:

[0212] (CH3)3Si-O-[Si(CH3)2O] 76 -[Si(CH3)R1O]3-[Si(CH3)R2O]7-Si(CH3)3;

[0213] in:

[0214] R1=-CH2CH2CH2OCH2C[CH2O(CH2CH2O)5H]3;

[0215] R2=-CH2CH2CH2O(CH2CH2O) 18 (CH2CHCH3O)5H;

[0216] Comparative Example 6

[0217] (1) Preparation of allyl tribromopentaerythritol

[0218] Allyl tribromopentaerythritol was prepared according to step (1) in Example 6.

[0219] (2) Preparation of allyl star polyether

[0220] According to step (2) in Example 6, an allyl group-containing star polyether was prepared.

[0221] (3) Preparation of star-shaped polyethers with aromatic groups at the end of allyl groups

[0222] According to step (3) in Example 6, a star-shaped polyether having an aromatic group at the end of the allyl group was prepared.

[0223] (4) Preparation of polyether silicone copolymers containing star-shaped polyethers

[0224] 35.32g of hydrogen-containing polymethylsiloxane from step (4) of Example 6, 32.35g of star-shaped polyether prepared in step (3) above, and 60.00g of toluene were added to the reactor, and heated to 90°C at normal pressure for 1h in the presence of 5ppm chloroplatinic acid catalyst and 40ppm N,N-dimethylaniline catalyst; 32.33g of allyl polyether from step (4) of Example 6 and 16ppm chloroplatinic acid catalyst were added, and the temperature was heated to 110°C for 6.0h, and the solvent was removed under reduced pressure to obtain a polyether organosilicon copolymer containing star-shaped polyether. Its structural characterization is as follows:

[0225] (CH3)3Si-O-[Si(CH3)2O] 43 -[Si(CH3)R1O]3-[Si(CH3)R2O]2-Si(CH3)3;

[0226] in:

[0227] R1=-CH2CH2CH2OCH2C[CH2O(CH2CH2O)4R3]3

[0228] R2=-CH2CH2CH2O(CH2CH2O) 15 (CH2CHCH3O)2H;

[0229]

[0230] Experimental Example 1

[0231] Examples 1-6 and Comparative Examples 1-6 are used as polyurethane foam stabilizers to produce rigid polyurethane foams, and their formulas are as follows:

[0232] Table 1 Rigid polyurethane foam foaming formula

[0233] Components Weight Polyether polyol 4110 50 servings Polyether polyol 635 20 servings Toluene diamine polyether polyol 410H 30 servings water 1.5 servings N,N-Dimethylcyclohexylamine 1.0 copy Pentamethyldiethylenetriamine 0.6 parts Polyurethane foam stabilizer 3.0 copies Cyclopentane 9 servings HFC-245fa 4.5 servings Black material: White material 120∶100

[0234] The rigid polyurethane foam prepared according to the above formula was subjected to performance tests, and the results are shown in Table 2, wherein the thermal conductivity (λ) was determined according to GB / T 10295-2008 Determination of steady-state thermal resistance and related properties of thermal insulation materials; the closed cell content was determined according to GB / T 10799-2008 Determination of volume percentage of open and closed cells in rigid foam plastics; the defects on the upper and lower surfaces of the foam and inside were scored on a scale of 1-10, with 1 indicating a large number of defects and severe damage to the foam, and 10 indicating no defects and no damage.

[0235] Table 2 Rigid polyurethane foam test results

[0236]

[0237]

[0238] The results in Table 2 show that compared with the polyether silicone copolymers not containing star-shaped polyether according to the present invention (Comparative Examples 1 and 4), the polyether silicone copolymers containing star-shaped polyether but without aromatic groups at the ends (Comparative Examples 2 and 5), and the polyether silicone copolymers containing star-shaped polyether with aromatic groups at the ends but with a higher proportion (Comparative Examples 3 and 6), the rigid polyurethane foam prepared from the polyether silicone copolymers of the present invention has significantly fewer surface and internal defects, and the number of cells per centimeter in the embodiments is more than that in the comparative examples. Therefore, the average pore size of the cells in the embodiments is smaller than that in the comparative examples, the closed cell rate of the foam is improved, and the thermal conductivity is significantly reduced.

[0239] Specifically, in Comparative Examples 1 and 4, allyl polyether is introduced only on the main chain of hydrogen-containing polymethylsiloxane, and since allyl polyether is a linear structure, its molecular weight is relatively large, which easily leads to a decrease in the compactness of the copolymer surface arrangement, and then the problem of bubble coarsening occurs. Therefore, the surface and internal defects of the rigid polyurethane foam prepared therefrom are significantly increased, the pore diameter increases, the foam closed cell rate decreases, and the thermal conductivity is significantly improved. In Comparative Examples 2 and 5, star-shaped polyether is introduced, but its end does not contain aromatic groups, at this time, the effect of Comparative Examples 2 and 5 is better than that of Comparative Examples 1 and 4, but due to the lack of aromatic groups, the emulsifying ability, foaming ability and cross-linking ability of the prepared organosilicon copolymer are not good enough, therefore, the surface and internal defects of the rigid polyurethane foam prepared therefrom are significantly increased, the pore diameter increases, the foam closed cell rate decreases, and the thermal conductivity is significantly improved. Comparative Examples 3 and 6 introduced polyethers containing aromatic groups at the end of the star, but the amount of the R1 group and the R2 group was not within the range of the present invention p / (p+q)=0.2-0.4, wherein the increase in the amount of R1 would result in an excessive amount of the star polyether, and the foam liquid film strength would be significantly reduced. Therefore, the rigid polyurethane foam prepared therefrom had more surface and internal defects, an increased pore size, a reduced foam closed cell rate, and a significantly improved thermal conductivity.

[0240] In summary, the polyether organosilicon copolymer containing star-shaped polyether provided by the present invention is obtained by grafting star-shaped polyether and allyl polyether with aromatic groups at the end of allyl groups on the main chain of hydrogen-containing polymethylsiloxane, and limiting the amount of R1 group and R2 group to p / (p+q)=0.2-0.4. The polyether organosilicon copolymer containing star-shaped polyether partially replaces the linear polyether with the star-shaped polyether, and the migration ability of the copolymer on the surface of the liquid film is increased. The star-shaped polyether mainly drags the liquid material in the shallow layer under the liquid film, and its ability to repair the thinning area is significantly enhanced, thereby reducing bubble rupture; at the same time, compared with the organosilicon copolymer with linear polyether as the side chain, the organosilicon copolymer containing star-shaped polyether overcomes the problem of bubble coarsening caused by the decrease in the compactness of the copolymer surface arrangement due to the large molecular weight of the linear polyether because each of its branches is shorter; the linear chain of the star-shaped polyether is fully combined with the liquid in the shallow layer under the liquid film to effectively improve the surface strength of the liquid surface, significantly enhance the shear resistance, and thus reduce surface defects. At the same time, aromatic groups are introduced at the ends of the star-shaped polyether to improve the emulsification ability of the reaction materials (isocyanate, polyol, foaming agent, etc.) during the preparation of the polyurethane foam, ensuring that the foaming reaction and the cross-linking reaction are carried out efficiently. The design and synthesis of the polyether silicone copolymer containing the star-shaped polyether effectively solves the problem that conventional polyether silicone copolymers cannot simultaneously reduce surface defects, open pores and coarsening, which makes it difficult to further reduce the thermal conductivity, significantly improves the quality of polyurethane foam, and prepares a rigid polyurethane foam with low surface defects, fine and uniform pores, and a high closed cell rate, which greatly reduces the thermal conductivity of the foam and improves the thermal insulation capacity of the foam. The preparation method of the polyether silicone copolymer containing star-shaped polyether provided by the present invention first prepares allyl tribromopentaerythritol; then, reacts with polyethylene glycol to obtain allyl star-shaped polyether; then, reacts with a chlorophenyl compound to obtain a star-shaped polyether with an aromatic group at the end of the allyl group; finally, the star-shaped polyether with an aromatic group at the end of the allyl group and the allyl polyether are grafted on the main chain of hydrogen-containing polymethylsiloxane to synthesize the polyether silicone copolymer containing star-shaped polyether. The whole synthesis process is simple to operate and easy to implement, and the preparation of the star-shaped polyether with an aromatic group at the end of the allyl group can be gradually realized, and the grafting ratio between the star-shaped polyether with an aromatic group at the end of the allyl group and the allyl polyether can also be limited, so as to prepare a polyether silicone copolymer containing star-shaped polyether that meets the requirements. The polyether silicone copolymer containing star-shaped polyether can be widely used in the preparation of foam stabilizers. The rigid polyurethane foam prepared by using the method has the characteristics of low surface defects, fine and uniform pores, high closed cell rate, low foam thermal conductivity, high thermal insulation capacity, etc., which can significantly improve the quality of polyurethane foam.

[0241] The above 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 variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A polyether organosilicon copolymer containing a star-shaped polyether, characterized in that: Its structural formula is as follows: Wherein, the value of m is 30-85, p+q=5-18 and p / (p+q)=0.2-0.4; R1=-CH2CH2CH2OCH2C[CH2O(CH2CH2O) a R3]3, a=3-8, R3 is an aromatic group; R2=-CH2CH2CH2O(CH2CH2O) x (CH2CHCH3O) y H,x=10-35,y=3-10。 2. The polyether organosilicon copolymer containing star-shaped polyether according to claim 1, characterized in that: The structural formula of the aromatic group is as follows:

3. A method for preparing a polyether organosilicon copolymer containing a star-shaped polyether as claimed in claim 1, characterized in that: It includes: Tribromopentaerythritol and allyl bromide are reacted to obtain allyl tribromopentaerythritol; reacting the allyl tribromopentaerythritol with polyethylene glycol to obtain an allyl star polyether; The allyl star polyether is reacted with a chlorinated phenyl compound to obtain a star polyether having an aromatic group at the end of the allyl group; The hydrogen-containing polymethylsiloxane, the star-shaped polyether with an aromatic group at the end of the allyl group and the allyl polyether are subjected to addition reaction to obtain a polyether organosilicon copolymer containing the star-shaped polyether.

4. The method for preparing a polyether organosilicon copolymer containing a star-shaped polyether according to claim 3, characterized in that: The preparation method of allyl tribromopentaerythritol comprises: mixing tribromopentaerythritol, allyl bromide, sodium hydride and a first solvent for reaction, controlling the temperature to rise to 25-30° C., and keeping the temperature for reaction for 4-6 hours to obtain a first reactant; Preferably, the molar ratio of the tribromopentaerythritol, the allyl bromide and the sodium hydride is 1:3-5:1.5-1.8; Preferably, the mass ratio of the total mass of the tribromopentaerythritol, the allyl bromide and the sodium hydride to the first solvent is 1:1.5-2.5; Preferably, the first solvent is tetrahydrofuran; Preferably, after the reaction is completed, a purification step is further included: the first reactant is added dropwise to a saturated aqueous solution of ammonium chloride at a temperature of 25-30° C., stirred for 2-4 hours, allowed to stand for stratification, the organic phase is washed three times with distilled water, and then dried with anhydrous sodium sulfate, filtered to remove the solvent, and purified to obtain allyl tribromopentaerythritol.

5. The method for preparing a polyether organosilicon copolymer containing a star-shaped polyether according to claim 3, characterized in that: The molar ratio of the allyl tribromopentaerythritol to the polyethylene glycol is 1:3.9-4.5; Preferably, the reaction of allyl tribromopentaerythritol and polyethylene glycol comprises: first dissolving the polyethylene glycol in a second solvent, adding sodium hydride, stirring the reaction, controlling the temperature to 25-30° C., keeping the temperature for reaction for 3-5 hours, then adding the allyl tribromopentaerythritol; heating to 90-110° C., stirring the reaction for 30-60 hours, and cooling to room temperature to obtain a second reactant; Preferably, the molar ratio of the polyethylene glycol to the sodium hydride is 1:1; Preferably, the mass ratio of the total mass of the polyethylene glycol, the sodium hydride and the allyl tribromopentaerythritol to the mass ratio of the second solvent is 1:3-6; Preferably, the second solvent is N,N-dimethylformamide; Preferably, after the reaction is completed, a purification step is further included: adding distilled water to the second reactant, stirring, and standing to separate the layers; extracting the aqueous phase with dichloromethane, adding anhydrous sodium sulfate to dry, filtering and removing the solvent, and purifying and vacuum drying to obtain the allyl star polyether.

6. The method for preparing a polyether organosilicon copolymer containing a star-shaped polyether according to claim 3, characterized in that: The molar ratio of the allyl star polyether to the chlorophenyl compound is 1:1.3-1.5; Preferably, the structure of the chlorophenyl compound contains only one chlorine atom connected to a benzene ring; Preferably, the reaction of the allyl star polyether and the chlorophenyl compound comprises: adding the allyl star polyether and a catalyst into a third solvent, stirring at 40-50° C. for 1-3 hours, adding the chlorophenyl compound, heating to 80-100° C. and continuing stirring for 60-80 hours to obtain a third reactant; Preferably, the catalyst is potassium hydroxide; Preferably, the amount of the catalyst is 0.5-2.0% of the total mass of the reaction raw materials; Preferably, the third solvent is dimethyl sulfoxide; Preferably, the mass ratio of the total mass of the allyl star polyether and the chlorinated phenyl compound to the mass ratio of the third solvent is 1:1-2; Preferably, after the reaction is completed, a purification step is further included: filtering the third reactant to remove the third solvent, completely dissolving the filter residue in water, extracting with chloroform, adding anhydrous sodium sulfate to dry, filtering, and purifying to obtain a star-shaped polyether with an aromatic group at the end of the allyl group.

7. The method for preparing a polyether organosilicon copolymer containing a star-shaped polyether according to claim 3, characterized in that: The molar ratio of the sum of the allyl double bonds in the star-shaped polyether having aromatic groups at the end of the allyl groups and the allyl polyether to the silicon-hydrogen bonds in the hydrogen-containing polymethylsiloxane is 1.2-1.6:1; Preferably, the addition reaction comprises: adding the hydrogen-containing polymethylsiloxane, the star-shaped polyether having an aromatic group at the end of the allyl group and the fourth solvent into a reactor, heating to 90-100° C. at normal pressure for reaction for 1 hour in the presence of a chloroplatinic acid catalyst and a co-catalyst; continuing to add the allyl polyether and the chloroplatinic acid catalyst, heating to 100-120° C. at normal pressure for reaction for 5-10 hours, and removing the solvent under reduced pressure to obtain a polyether organosilicon copolymer containing a star-shaped polyether; Preferably, the fourth solvent is toluene; Preferably, the total mass ratio of the hydrogen-containing polymethylsiloxane, the star-shaped polyether having an aromatic group at the end of the allyl group, the allyl polyether and the fourth solvent is 1:0.5-1.

8. Use of the polyether organosilicon copolymer containing star-shaped polyethers as claimed in any one of claims 1 to 2 or the polyether organosilicon copolymer containing star-shaped polyethers as claimed in any one of claims 3 to 7 in the preparation of foam stabilizers.

9. A foam stabilizer, characterized in that The invention comprises the polyether organosilicon copolymer containing star-shaped polyether as claimed in any one of claims 1 to 2 or the polyether organosilicon copolymer containing star-shaped polyether prepared by the preparation method of the polyether organosilicon copolymer containing star-shaped polyether as claimed in any one of claims 3 to 7.

10. A rigid polyurethane foam, characterized in that: Its components include the foam stabilizer as claimed in claim 9.

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