阅读说明：本技术 一种聚醚-有机硅复合尼龙弹性体及其制备方法 (Polyether-organic silicon composite nylon elastomer and preparation method thereof ) 是由 王为国 王健 王朝进 田国锋 亓玉刚 毕燕 张全福 于 2021-06-18 设计创作，主要内容包括：本发明公开了一种聚醚-有机硅复合尼龙弹性体及其制备方法,将聚醚产物与有机硅聚合物引入尼龙合成反应过程中,制备成聚醚-有机硅尼龙复合弹性体。本发明提出以机硅类为软段制备了新型尼龙弹性体,与传统聚醚为软段的弹性体相比,本发明制备的新型尼龙弹性体具有柔韧性更佳,断裂伸长率更高的优异性能。(The invention discloses a polyether-organic silicon composite nylon elastomer and a preparation method thereof. Compared with the traditional elastomer with polyether as the soft segment, the novel nylon elastomer prepared by the invention has excellent performances of better flexibility and higher elongation at break.)

1. The polyether-organosilicon composite nylon elastomer is characterized by comprising the following raw materials in parts by weight:

50 parts of nylon 66 salt, 10 parts of acidifier, 5-35 parts of low-viscosity organic silicon polymer, 5-35 parts of low-viscosity polyether product, 0.03-0.05 part of catalyst, 0.03-0.05 part of brightener and 0.03-0.05 part of antioxidant.

2. The polyether-silicone composite nylon elastomer of claim 1, wherein the low viscosity silicone polymer is a hydroxyl terminated polydimethylsiloxane having a viscosity of 500 mpa.s.

3. The polyether-silicone composite nylon elastomer of claim 1, wherein the acidifying agent is one of adipic acid, glutaric acid, and dodecanedioic acid.

4. The polyether-silicone composite nylon elastomer of claim 1, wherein the low viscosity polyether product is polytetramethylene glycol having a viscosity of 1000 mpa.s.

5. The polyether-silicone composite nylon elastomer of claim 1, wherein the catalyst is one or two of potassium acetate, dibutyltin dilaurate, and tetrabutyl titanate.

6. The polyether-silicone composite nylon elastomer of claim 1, wherein the whitening agent is one of phosphorous acid, sodium hypophosphite, and triphenyl phosphite.

7. The polyether-silicone composite nylon elastomer according to claim 1, wherein the antioxidant is one or two of tris [ 2.4-di-tert-butylphenyl ] phosphite, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, and the like.

8. The method for preparing the polyether-silicone composite nylon elastomer according to any one of claims 1 to 7, comprising the steps of:

1) adding the nylon 66 salt in the weight part into softened water to prepare a nylon 66 salt solution with the final concentration of 50-70%, and adding the acidifier in the weight part to obtain an acidified nylon 66 salt solution;

2) mixing the low-viscosity polyether product and the low-viscosity organic silicon polymer in parts by weight to obtain a blended soft segment substance;

3) adding the blended soft segment substance prepared in the step 2) into the acidified nylon 66 salt solution prepared in the step 1), adding the catalyst, the whitening agent and the antioxidant in parts by weight, placing the mixture into a polymerization kettle, maintaining the pressure to 1.8-2.2Mpa, raising the temperature to 210-230 ℃, reducing the pressure, discharging when the material temperature is 260-280 ℃, cooling with warm water, and pelletizing to obtain the polyether-organic silicon composite nylon elastomer.

Technical Field

The invention relates to a polyether-organic silicon composite nylon elastomer and a preparation method thereof, belonging to the field of nylon material synthesis.

Background

Nylon is a hard material with high strength, high wear resistance and high hardness, is mainly applied to the field of engineering plastics with higher requirements on strength, and is limited in application in the field of elastomers, particularly in the field of high-flexibility elastomer materials due to lower elasticity of the high-flexibility elastomer materials. In order to further expand the application range of the nylon elastomer, the nylon elastomer is a product which is relatively hot to research in the industry at present and has relatively strong applicability.

The nylon elastomer is a block copolymer, which is composed of a crystalline nylon hard segment with a high melting point and an amorphous or amorphous polyester or polyether soft segment. Their chemical composition, fragment length and the ratio between them determine the physical and chemical properties of such materials. The nylon elastomer has high strength, high toughness, good elasticity, low specific gravity, good bending fatigue resistance, good wear resistance and good low-temperature performance, and can be widely applied to automobiles, sports goods, medical supplies, sealing elements, mechanical parts and the like.

The conventional nylon elastomer is generally produced by carrying out block copolymerization polymerization by taking nylon as a hard segment and ethers as a soft segment, the product has the characteristics of both rubber and thermoplastic plastics, the common nylon elastomer is prepared by copolymerizing nylon 12 and polyether polyol, and the commercialized products comprise Pebax XX33 series products of Arkema company in France and Vestamid E series products of Envonik company in Germany. However, with the intensive research on nylon elastomers, products using ethers as soft segments have problems of low elongation at break, low elasticity, low temperature resistance, and the like.

Disclosure of Invention

The invention overcomes the defects of the prior art and provides the polyether-organic silicon composite nylon elastomer and the preparation method thereof.

The polyether-organosilicon composite nylon elastomer comprises the following raw materials in parts by weight:

50 parts of nylon 66 salt, 10 parts of acidifier, 5-35 parts of low-viscosity organic silicon polymer, 5-35 parts of low-viscosity polyether product, 0.03-0.05 part of catalyst, 0.03-0.05 part of brightener and 0.03-0.05 part of antioxidant;

further, the low-viscosity organic silicon polymer is hydroxyl-terminated polydimethylsiloxane with the viscosity of 500 Mpa.s.

Further, the acidifying agent is one of adipic acid, glutaric acid and dodecanedioic acid.

Further, the low-viscosity polyether product is polytetramethylene glycol with the viscosity of 1000MPa.

Further, the catalyst is one or two of potassium acetate, dibutyltin dilaurate and tetrabutyl titanate.

Further, the whitening agent is one of phosphorous acid, sodium hypophosphite and triphenyl phosphite.

Further, the antioxidant is one or two of tris [2, 4-di-tert-butylphenyl ] phosphite, N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, and the like.

Further, the preparation method of the polyether-organic silicon composite nylon elastomer comprises the following steps:

1) adding the nylon 66 salt in the weight part into softened water to prepare a nylon 66 salt solution with the final concentration of 50-70%, and adding the acidifier in the weight part to obtain an acidified nylon 66 salt solution;

2) mixing the low-viscosity polyether product and the low-viscosity organic silicon polymer in parts by weight to obtain a blended soft segment substance;

3) adding the blended soft segment substance prepared in the step 2) into the acidified nylon 66 salt solution prepared in the step 1), adding the catalyst, the whitening agent and the antioxidant in parts by weight, placing the mixture into a polymerization kettle, maintaining the pressure to 1.8-2.2Mpa, raising the temperature to 210-230 ℃, reducing the pressure, discharging when the material temperature is 260-280 ℃, cooling with warm water, and pelletizing to obtain the polyether-organic silicon composite nylon elastomer.

This patent uses nylon 66 as basic nylon materials, and is with low costs, and the hardness is higher for long carbon chain nylon, and its key is exactly the hardness that effectively reduces nylon 66, increases its toughness. The toughness and softness of the organosilicon material after polymerization by the catalyst are much higher than those of the polymerized polyether, but the polymerization activity of the organosilicon is weaker than that of the polyether material, so the organosilicon and polyether composite soft segment material is utilized in the patent.

Has the advantages that:

(1) compared with the traditional elastomer with polyether as the soft segment, the novel nylon elastomer prepared by the invention has excellent performances of better flexibility and higher elongation at break.

(2) The nylon 66 salt solution is used as a base material, so that the cost is greatly reduced; the finished product greatly improves the hardness of the nylon 66 product.

(3) This patent adds into nylon 66 material with polyether class, organosilicon class material complex, and has the accuracy requirement to the viscosity of two kinds of additives, can effectively reduce the product polymerization degree of difficulty, and the cost reduces by a wide margin, and has solved the organosilicon class polymer activity that the weight is big effectively and low, is difficult for participating in the problem of polymerization.

(4) Although the organic silicon substance is used as an addition part, the selected hydroxyl-terminated polydimethylsiloxane is hydroxyl-terminated, and a silane coupling agent is not used as a linking agent.

Detailed Description

In order to make the technical solutions in the present application better understood, the present invention is further described below with reference to examples, which are only a part of examples of the present application, but not all examples, and the present invention is not limited by the following examples.

The first embodiment is as follows:

dissolving 5000g of nylon 66 salt by softened water, adjusting the concentration of the solution to 65%, adding 1000g of adipic acid for acidification after the solution is completely dissolved, and adjusting the acidity for later use; uniformly mixing 500g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 500Mpa.s and 3500g of polytetramethylene glycol with the viscosity of 1000 Mpa.s; uniformly mixing the acidified nylon 66 salt with the mixed hydroxyl-terminated polydimethylsiloxane and polytetramethylene glycol, adding 3g of potassium acetate, 3g of tetrabutyl titanate, 3g of phosphorous acid and 3g of antioxidant 1098, putting into a polymerization kettle, keeping the temperature and the pressure to 215 ℃ and 2.0MPa, then gradually reducing the pressure to normal pressure, expelling gas for 1 hour at the normal pressure, maintaining the vacuum degree to-0.003 MPa for 1 hour, and then discharging when the material temperature reaches 255 ℃ to obtain the nylon 66 elastomer.

Example two:

dissolving 5000g of nylon 66 salt by softened water, adjusting the concentration of the solution to 65%, adding 1000g of adipic acid for acidification after the solution is completely dissolved, and adjusting the acidity for later use; uniformly mixing 1000g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 500Mpa.s and 3000g of polytetramethylene glycol with the viscosity of 1000 Mpa.s; uniformly mixing the acidified nylon 66 salt with the mixed hydroxyl-terminated polydimethylsiloxane and polytetramethylene glycol, adding 3g of potassium acetate, 3g of tetrabutyl titanate, 3g of phosphorous acid and 3g of antioxidant 1098, putting into a polymerization kettle, keeping the temperature and the pressure to 215 ℃ and 2.0MPa, then gradually reducing the pressure to normal pressure, expelling gas for 1 hour at the normal pressure, maintaining the vacuum degree to-0.003 MPa for 1 hour, and then discharging when the material temperature reaches 255 ℃ to obtain the nylon 66 elastomer.

Example three:

dissolving 5000g of nylon 66 salt by softened water, adjusting the concentration of the solution to 65%, adding 1000g of adipic acid for acidification after the solution is completely dissolved, and adjusting the acidity for later use; uniformly mixing 1500g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 500Mpa.s and 2500g of polytetramethylene glycol with the viscosity of 1000 Mpa.s; uniformly mixing the acidified nylon 66 salt with the mixed hydroxyl-terminated polydimethylsiloxane and polytetramethylene glycol, adding 3g of potassium acetate, 3g of tetrabutyl titanate, 3g of phosphorous acid and 3g of antioxidant 1098, putting into a polymerization kettle, keeping the temperature and the pressure to 215 ℃ and 2.0MPa, then gradually reducing the pressure to normal pressure, expelling gas for 1 hour at the normal pressure, maintaining the vacuum degree to-0.003 MPa for 1 hour, and then discharging when the material temperature reaches 255 ℃ to obtain the nylon 66 elastomer.

Example four:

dissolving 5000g of nylon 66 salt by softened water, adjusting the concentration of the solution to 65%, adding 1000g of adipic acid for acidification after the solution is completely dissolved, and adjusting the acidity for later use; uniformly mixing 2000g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 500Mpa.s and 2000g of polytetramethylene glycol with the viscosity of 1000 Mpa.s; uniformly mixing the acidified nylon 66 salt with the mixed hydroxyl-terminated polydimethylsiloxane and polytetramethylene glycol, adding 3g of potassium acetate, 3g of tetrabutyl titanate, 3g of phosphorous acid and 3g of antioxidant 1098, putting into a polymerization kettle, keeping the temperature and the pressure to 215 ℃ and 2.0MPa, then gradually reducing the pressure to normal pressure, expelling gas for 1 hour at the normal pressure, maintaining the vacuum degree to-0.003 MPa for 1 hour, and then discharging when the material temperature reaches 255 ℃ to obtain the nylon 66 elastomer.

Example five:

dissolving 5000g of nylon 66 salt by softened water, adjusting the concentration of the solution to 65%, adding 1000g of adipic acid for acidification after the solution is completely dissolved, and adjusting the acidity for later use; uniformly mixing 2500g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 500Mpa.s and 1500g of polytetramethylene glycol with the viscosity of 1000 Mpa.s; uniformly mixing the acidified nylon 66 salt with the mixed hydroxyl-terminated polydimethylsiloxane and polytetramethylene glycol, adding 3g of potassium acetate, 3g of tetrabutyl titanate, 3g of phosphorous acid and 3g of antioxidant 1098, putting into a polymerization kettle, keeping the temperature and the pressure to 215 ℃ and 2.0MPa, then gradually reducing the pressure to normal pressure, expelling gas for 1 hour at the normal pressure, maintaining the vacuum degree to-0.003 MPa for 1 hour, and then discharging when the material temperature reaches 255 ℃ to obtain the nylon 66 elastomer.

The key performance index pairs for the products produced by the polymerization of the above examples are as follows:

TABLE 1 comparison table of key performance indexes of products in examples

Serial number	Impact performance	Hardness of	Elongation at break
				Example one	25JNB	111A	150％
Example two	25JNB	102A	240％
				EXAMPLE III	25JNB	91A	310％
Example four	25JNB	79A	390％
				EXAMPLE five	25JNB	68A	460％

Note: this patent detection standard: impact performance (GB/T1043-; hardness (GB/T2411-; elongation at break (GB/T1040-2006).

The patent provides a preparation of polyether-organosilicon composite nylon elastomer, and shows that 50 parts by mass of nylon 66 salt, 10 parts by mass of adipic acid acidifying agent, 20 parts by mass of 500Mpa.s hydroxyl-terminated polydimethylsiloxane and 20 parts by mass of polytetramethylene glycol with the viscosity of 1000Mpa.s can obtain a product which is more in line with the requirement and expectation, the hardness is lower than 80A, the elongation at break is close to 400%, and the performance is excellent.