Amine polyether polyol as well as preparation method and application thereof

Abstract

The invention discloses amine polyether polyol as well as a preparation method and application thereof, and belongs to the technical field of polyol. According to the technical scheme, the amine polyether polyol comprises an amine initiator, a catalyst, an epoxide and an adsorbent, and the synthesis method comprises the following steps: 1) adding the amine initiator and the catalyst into a reactor, introducing inert gas into a material for replacement, adding the epoxide into the mixture, and carrying out anionic polymerization reaction; (2) carrying out heat preservation and curing reaction at 80-150 DEG C for 3-6 hours, and after the reaction is completed, heating and degassing at 90-110 DEG C to obtain a polyether polyol crude product; and 3) adsorbing the polyether polyol crude product with an adsorbent, heating for dehydration, and filtering to obtain the amine polyether polyol finished product. The amine polyether polyol synthesized by the method disclosed by the invention is high in functionality, the synthesis process conditions are easy to control, and the product is high in reaction activity and catalytic activity and stable in storage, and can be used as a cross-linking agent and a catalyst.

Description

Technical Field

[0001] The invention belongs to the technical field of polyols, and specifically relates to an amine polyether polyol and a preparation method and application thereof. Background Art

[0002] Polyurethane (PU) is an important type of synthetic resin, which has a repeating structural unit of carbamate and can be used as foam plastics, low-speed tires, adhesives, coatings, synthetic leather, waterproofing, gaskets, air cushions and paving materials, etc. It is widely used. Polyurethane foam plastic (PUF) is an important variety of polyurethane synthetic materials, which is widely used in various insulation, shockproof, soundproof, lightweight structural parts and cushions, packaging, automotive interior parts, etc. It occupies an important position in the plastics industry.

[0003] With the development of polyurethane industrial manufacturing technology, people's requirements for polyurethane foam products have gradually shifted from single physical performance indicators to requirements for comprehensive performance such as product environmental protection performance and functionalization. Most polyurethane foam products use catalysts in the foaming process, among which amine catalysts are a type of catalyst commonly used in polyurethane products. Amine catalysts only catalyze foaming during the preparation of polyurethane foam and do not participate in the foaming reaction. After the foam is prepared, such small molecule amine catalysts will gradually penetrate and migrate to the surface of the foam product, and then gradually diffuse into the environment. Most automotive interior materials are polyurethane products. The released amine small molecule catalysts can cause the car windshield to fog and cause severe new car odor. Such problems also exist in the furniture industry. Therefore, the safety and environmental protection issues caused by amine small molecule catalysts in polyurethane foam products have received more and more attention. Summary of the invention

[0004] The invention provides an amine polyether polyol, which has high functionality, easy-to-control synthesis process conditions, high product reaction activity and catalytic activity. The polyether polyol synthesized by using the amine polyether as a catalyst has stable storage and can be used as a crosslinking agent and catalyst.

[0005] The technical solution of the present invention is:

[0006] In a first aspect, an amine polyether polyol is disclosed, comprising the following raw materials in parts by weight:

[0007] Amine initiator 10-90 parts

[0008] Catalyst 0.05~0.3 parts

[0009] Epoxide 10-90 parts

[0010] Adsorbent 0.1 to 1 part.

[0011] Preferably, the number average molecular weight of the amine polyether polyol is in the range of 103-1000.

[0012] Preferably, the amine initiator is one or both of diethylenetriamine and tetraethylenepentamine, and the catalyst is an alkali metal catalyst.

[0013] Preferably, the epoxide is one or more of ethylene oxide, propylene oxide and butylene oxide.

[0014] Preferably, the adsorbent is aluminum silicate or magnesium silicate or magnesium aluminum silicate.

[0015] In a second aspect, a method for synthesizing the amine polyether polyol is disclosed, comprising the following steps:

[0016] 1) In a reactor, an amine initiator and a catalyst are added, nitrogen is introduced into the material for replacement, and then epoxide is added to the mixture to carry out anionic polymerization;

[0017] 2) Keep the reaction at 80-150° C. for 3-6 hours until the reaction is complete, and then heat to 90-110° C. for degassing to obtain a crude polyether polyol product;

[0018] 3) The crude polyether polyol product is adsorbed by an adsorbent, heated for dehydration, and filtered to obtain the finished amine polyether polyol product.

[0019] Preferably, the temperature of the anionic polymerization reaction in step 1) is 80-150° C. and the pressure is 0-0.6 MPa; nitrogen replacement is performed in step 1), and after the oxygen content is less than 100 ppm, the reaction mixture is evacuated to -0.098 MPa and epoxide is added.

[0020] Preferably, the reaction temperature for heating and dehydration in step 3) is 90-125° C., and the water content is controlled at 0-0.05% by mass.

[0021] The third aspect discloses the use of the amine polyether polyol in the preparation of rigid foam polyurethane, semi-rigid foam polyurethane and polyurethane elastomer.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The amine polyether polyol synthesized by the method disclosed in the present invention has high functionality, easy control of synthesis process conditions, high product reaction activity and catalytic activity, stable storage, and can be used as a crosslinking agent and catalyst. When the polyether polyol synthesized by the amine polyether catalysis is used in the production of polyurethane foam products, the amount of amine catalyst used in the downstream product processing process can be significantly reduced, the content of volatile organic matter in the product can be effectively reduced, and the production cost can be effectively reduced for the production enterprise. It is mainly used in the fields of rigid foam polyurethane, semi-rigid foam polyurethane and polyurethane elastomer. DETAILED DESCRIPTION

[0024] In order to enable those skilled in the art to better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments.

[0025] Example 1

[0026] This embodiment provides a method for preparing an amine polyether polyol, which is as follows:

[0027] 1) Add 262.4g of diethylenetriamine and 3g of potassium hydroxide to a stainless steel kettle, replace with nitrogen, and when the oxygen content in the kettle is less than 100ppm, evacuate to -0.098MPa, heat to 90°C, maintain the temperature in the kettle at 100°C and the pressure at 0.3MPa, and continuously add 737.6g of propylene oxide;

[0028] 2) After the propylene oxide feeding is completed, the mixture is kept at 100° C. for aging reaction for 3 hours. After the reaction is complete, the mixture is heated to 90° C. and vacuum-dried to remove small molecular byproducts generated by the reaction to obtain a crude polyether polyol product;

[0029] 3) Add 50g of water and 2g of magnesium aluminum silicate, heat up for dehydration, the reaction temperature of dehydration is increased from 90°C to 125°C, the water content is controlled at 0.05% by mass, and filtered to obtain the refined polyether polyol product a. The test results of product a are shown in Table 1: In Table 1, the hydroxyl value is calculated based on the mass of KOH that can be neutralized per gram of product.

[0030] Example 2

[0031] The difference from Example 1 is that in Example 2, propylene oxide is replaced by ethylene oxide, the input mass remains unchanged, and other conditions remain unchanged to obtain a refined polyether polyol product b. The test results of product b are shown in Table 1.

[0032] Example 3

[0033] This embodiment provides a method for preparing an amine polyether polyol, which is as follows:

[0034] 1) Add 151g of diethylenetriamine and 3g of potassium hydroxide to a stainless steel kettle, replace with nitrogen, and when the oxygen content in the kettle is less than 100ppm, evacuate to -0.098MPa, heat to 90°C, maintain the temperature in the kettle at 100°C and the pressure at 0.3MPa, and continuously add 849g of propylene oxide;

[0035] 2) After the propylene oxide feeding is completed, the mixture is kept at 100° C. for aging reaction for 3 hours. After the reaction is complete, the mixture is heated to 90° C. and vacuum-dried to remove the small molecular byproducts generated by the reaction to obtain a crude polyether polyol product;

[0036] 3) Add 50g of water and 2g of magnesium aluminum silicate, heat up for dehydration, the reaction temperature of dehydration is increased from 90°C to 125°C, the water content is controlled at 0.05% by mass, and filtered to obtain the refined polyether polyol product C. The test results of product C are shown in Table 1: In Table 1, the hydroxyl value is calculated based on the mass of KOH that can be neutralized per gram of product.

[0037] Example 4

[0038] The difference from Example 3 is that in Example 4, propylene oxide is replaced by ethylene oxide, the input mass remains unchanged, and other conditions remain unchanged to obtain a refined polyether polyol product d. The test results of product d are shown in Table 1.

[0039] Table 1 Test results of product ad

[0040]

[0041] Example 5

[0042] Product a prepared in Example 1 was used as a catalyst to prepare a rigid foam polyether polyol. The specific method is as follows:

[0043] 1) 50 g of diethylene glycol, 328.6 g of sucrose, 7.7 g of amine catalyst (product a) and 42.1 g of water were added to a stainless steel kettle, and nitrogen was replaced. When the oxygen content in the kettle was measured to be less than 100 ppm, the kettle was evacuated to -0.098 MPa, the temperature was raised to 95° C., 220.7 g of propylene oxide was introduced, the reaction temperature was maintained at 95° C., and the pressure in the reactor was maintained at 0.3 MPa. After the propylene oxide feeding was completed, the reaction was kept at 95° C. for 3 h. The reaction was completed to obtain a polyether polyol intermediate.

[0044] 2) The polyether polyol intermediate was subjected to a heating and dehydration operation, the temperature was required to be 100°C, and nitrogen bubbling was used for dehydration. When the water content was less than 0.5%, 6.1g of amine catalyst (product a) and 331.6g of palm oil were added. When the temperature was above 110°C, propylene oxide was continuously fed, and the reaction temperature was controlled at 110°C and the pressure was 0.3MPa. After 442.7g of propylene oxide was fed, the temperature was maintained at 120°C, ripened for 3h, and then degassed for 1h, and the hard foam polyether polyol product e was obtained, without post-treatment. The test results of product e are shown in Table 2.

[0045] Example 6

[0046] Different from Example 5, product a in Example 5 is replaced with an equal amount of product b prepared in Example 2 to prepare a rigid foam polyether polyol product f without post-treatment. The test results of product f are shown in Table 2.

[0047] Example 7

[0048] This comparative example provides a method for preparing a rigid foam polyether polyol using the product C in the above Example 3 as a catalyst, as follows:

[0049] 1) 50 g of diethylene glycol, 328.6 g of sucrose, 7.7 g of amine catalyst (product c) and 42.1 g of water were added to a stainless steel kettle, and nitrogen was replaced. When the oxygen content in the kettle was measured to be less than 100 ppm, the kettle was evacuated to -0.098 MPa, the temperature was raised to 95° C., 220.7 g of propylene oxide was introduced, and the temperature in the kettle was maintained at 95° C. and the pressure was 0.3 MPa. After the propylene oxide feeding was completed, the kettle was kept warm and aged for 3 h at 95° C. The reaction was completed to obtain a polyether polyol intermediate.

[0050] 2) The polyether polyol intermediate was subjected to a heating and dehydration operation, the temperature was required to be 100°C, and nitrogen bubbling was used for dehydration. When the water content was less than 0.5%, 6.1g of amine catalyst (product c) and 331.6g of palm oil were added. When the temperature was above 110°C, 442.7g of propylene oxide was continuously fed, and the temperature in the kettle was maintained at 110°C and the pressure was 0.3MPa. After the propylene oxide was added, the temperature was maintained at 120°C, and the kettle was aged for 3h, and then degassed for 1h, and the hard foam polyether polyol product g was obtained without post-treatment. The test results of product g are shown in Table 2.

[0051] Example 8

[0052] Different from Example 7, the product c in Example 7 is replaced by an equal amount of the product d prepared in Example 4 to prepare a rigid foam polyether polyol product h without post-treatment. The test results of product h are shown in Table 2.

[0053] Comparative Example 1

[0054] Different from Example 5, the product a in Example 5 is replaced with an equal amount of commercially available dimethylamine as a catalyst to prepare product i without post-treatment. The detection results of product i are shown in Table 2.

[0055] Comparative Example 2

[0056] This comparative example uses solid potassium hydroxide as a catalyst to prepare a synthetic method for rigid foam polyether polyol, as follows:

[0057] 1) 50g of diethylene glycol, 328.6g of sucrose, 2.1g of potassium hydroxide and 42.1g of water were added to a stainless steel kettle, and nitrogen was replaced. When the oxygen content in the kettle was measured to be less than 100ppm, the kettle was evacuated to -0.098MPa, the temperature was raised to 95°C, 220.7g of propylene oxide was introduced, and the temperature in the kettle was maintained at 95°C and the pressure was 0.3MPa. After the propylene oxide feeding was completed, the kettle was kept warm and aged for 3h at 95°C. The reaction was completed to obtain a polyether polyol intermediate.

[0058] 2) The polyether polyol intermediate is subjected to a heating and dehydration operation, the temperature is required to be 100°C, and nitrogen bubbling is used for dehydration. When the water content is less than 0.5%, 2.1g potassium hydroxide and 331.6g palm oil are added. When the temperature is above 110°C, 442.7g propylene oxide is continuously fed, and the temperature in the kettle is maintained at 110°C and the pressure is maintained at 0.3MPa. After the addition of propylene oxide, the temperature in the kettle is maintained at 110°C and the pressure is maintained at 0.3MPa, and then degassing is performed for 1h to obtain a crude polyether polyol;

[0059] 3) Add 60 g of water and 2.5 g of magnesium aluminum silicate to the crude polyether polyol, heat up for dehydration, the reaction temperature for dehydration is 90-125° C., the moisture content is controlled at 0.05% by mass, and filter to obtain a hard foam polyether polyol product j. The test results of product j are shown in Table 2.

[0060] Table 2

[0061]

[0062] The rigid foam polyether polyols prepared in Examples 5-8 and Comparative Examples 1-2 were subjected to foaming experiments respectively. The specific process was as follows: a combined polyether polyol was prepared respectively, with a mass ratio of 100 parts of the rigid foam polyether polyols prepared in Examples 5-8 and Comparative Examples 1-2, 2 parts of silicone oil, and 5 parts of cyclopentane as a foaming agent, and then foamed with isocyanate (PAPI) at a mass ratio of 1:1. The foaming test results obtained using the products of different comparative examples are shown in Table 3.

[0063] Table 3

[0064]

[0065]

[0066] In Comparative Example 2, because no amine catalyst is used in the production process, the rise time and gel time are significantly longer when the foaming experiment is carried out, and the post-processing refining process is required when the rigid foam polyether polyol is produced in Comparative Example 2, and the production process is relatively complicated; the rigid foam polyether polyol produced by using the products of Examples 1-4 as catalysts, the foam density and compression strength are equivalent to those of Comparative Example 1; and in the foaming experiments carried out in Examples 5 and 6, the shrinkage rate is lower than the shrinkage rate of Comparative Example 1. The amine polyether polyol synthesized by the method disclosed in the present invention has high functionality, easy control of synthesis process conditions, high product reaction activity and catalytic activity, stable storage, and can be used as a crosslinking agent and catalyst. When the polyether polyol synthesized by the amine polyether catalysis is used in the production of polyurethane foam products, the amount of amine catalyst used in the downstream product processing process can be significantly reduced, the content of volatile organic matter in the product can be effectively reduced, and the production cost can also be effectively reduced for the production enterprise. It is mainly used in the fields of rigid foam polyurethane, semi-rigid foam polyurethane and polyurethane elastomer.

[0067] Although the present invention has been described in detail by combining the preferred embodiments, the present invention is not limited thereto. Without departing from the spirit and essence of the present invention, a person of ordinary skill in the art may make various equivalent modifications or substitutions to the embodiments of the present invention, and these modifications or substitutions shall be within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. Amine polyether polyol, characterized in that: The invention comprises the following raw materials in parts by weight: Amine initiator 10-90 parts Catalyst 0.05~0.3 parts Epoxide 10-90 parts Adsorbent 0.1 to 1 part.

2. The amine polyether polyol according to claim 1, characterized in that: The number average molecular weight of the amine polyether polyol is in the range of 103-1000.

3. The amine polyether polyol according to claim 1, characterized in that: The amine initiator is one or two of diethylenetriamine and tetraethylenepentamine, and the catalyst is an alkali metal catalyst.

4. The amine polyether polyol according to claim 1, characterized in that: The epoxide is one or more of ethylene oxide, propylene oxide and butylene oxide.

5. The amine polyether polyol according to claim 1, characterized in that: The adsorbent is aluminum silicate, magnesium silicate or magnesium aluminum silicate.

6. The method for synthesizing an amine polyether polyol according to any one of claims 1 to 5, characterized in that: The following steps are involved: 1) In a reactor, an amine initiator and a catalyst are added, nitrogen is introduced into the material for replacement, and then epoxide is added to the mixture to carry out anionic polymerization; 2) Keep the reaction at 80-150° C. for 3-6 hours until the reaction is complete, and then heat to 90-110° C. for degassing to obtain a crude polyether polyol product; 3) The crude polyether polyol product is adsorbed by an adsorbent, heated for dehydration, and filtered to obtain the finished amine polyether polyol product.

7. The method for synthesizing an amine polyether polyol as claimed in claim 6, characterized in that: In step 1), the temperature of the anionic polymerization reaction is 80-150° C. and the pressure is 0-0.6 MPa. In step 1), nitrogen replacement is performed. After the oxygen content is less than 100 ppm, the reaction is evacuated to -0.098 MPa and epoxide is added.

8. The method for synthesizing an amine polyether polyol as claimed in claim 6, characterized in that: The reaction temperature of the heating and dehydration in step 3) is 90-125° C., and the water content is controlled at 0-0.05% by mass.

9. Use of the amine polyether polyol according to any one of claims 1 to 5 in the preparation of rigid foam polyurethane, semi-rigid foam polyurethane and polyurethane elastomer.

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