阅读说明：本技术 一种性能稳定的改性氨基硅油的制备方法 (Preparation method of modified amino silicone oil with stable performance ) 是由 张小伟 田飞 于 2020-12-30 设计创作，主要内容包括：本发明属于日用化学品技术领域,更具体的涉及一种性能稳定的改性氨基硅油的制备方法。以单烯丙基封端聚氧乙烯聚氧丙烯环氧基醚和硅烷偶联剂为原料制备出氨基聚醚,然后氨基聚醚与八甲基环四硅氧烷(D4)为原料制备出了性能稳定的改性氨基硅油。本发明制备出的改性氨基硅油在酸(pH＝5-6)、碱(pH＝7.5-8.5)和中性条件下均呈现乳液状态,织物吸水性为0.3/s。(The invention belongs to the technical field of daily chemicals, and particularly relates to a preparation method of modified amino silicone oil with stable performance. The modified amino silicone oil with stable performance is prepared by taking monoallyl-terminated polyoxyethylene polyoxypropylene epoxy ether and a silane coupling agent as raw materials to prepare amino polyether, and then taking the amino polyether and octamethylcyclotetrasiloxane (D4) as raw materials. The modified amino silicone oil prepared by the invention is in an emulsion state under the conditions of acid (pH is 5-6), alkali (pH is 7.5-8.5) and neutrality, and the water absorption of the fabric is 0.3/s.)

1. A preparation method of modified amino silicone oil with stable performance is characterized by comprising the following steps: the modified amino silicone oil with stable performance is prepared by taking monoallyl-terminated polyoxyethylene polyoxypropylene epoxy ether and a silane coupling agent as raw materials to prepare amino polyether, and then taking the amino polyether and octamethylcyclotetrasiloxane (D4) as raw materials.

2. The method of claim 1, wherein: the method specifically comprises the following steps:

1) synthesis of aminopolyethers

Reacting mono allyl terminated polyoxyethylene polyoxypropylene epoxy ether with silane coupling agent N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane in an alcohol solvent, and removing the alcohol solvent by reduced pressure distillation after the reaction is finished to obtain amino polyether;

2) synthesis of modified amino silicone oil

The amino polyether and octamethylcyclotetrasiloxane generate modified amino silicone oil under the catalytic action of inorganic base at 60-90 ℃.

3. The method of claim 2, wherein: the molar ratio of the monoallyl-terminated polyoxyethylene polyoxypropylene epoxy ether in the step 1) to the N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane is 1: 1.

4. the method of claim 2, wherein: the step 1) also comprises a purification step of the amino polyether, specifically, the amino polyether is added into n-heptane, standing and layering are carried out, the upper layer is discarded, and the lower layer is the purified amino polyether.

5. The method of claim 2, wherein: the dosage of the aminopolyether in the step 2) is 5 to 10 percent of the weight of the octamethylcyclotetrasiloxane.

6. The method of claim 2, wherein: and 2) further comprising a purification step of modified amino silicone oil, specifically, dissolving the modified amino silicone oil by using dichloromethane, then dropwise adding anhydrous methanol, adding the anhydrous methanol to generate white floccules at the lower layer of the mixed solution, removing the upper layer of the mixed solution, repeating the steps for 3 times, and distilling the methanol and the dichloromethane in the white floccules to obtain the purified modified amino silicone oil.

Technical Field

The invention belongs to the technical field of daily chemicals, and particularly relates to a preparation method of modified amino silicone oil with stable performance.

Background

The common amino silicone oil is a softener widely applied in the textile industry, has the properties of improving the hand feeling of fabrics, making the fabrics soft, smooth and crease-resistant, is harmless to human bodies, and is well received. However, the amino silicone oil enables the fabric fiber to present certain water combing property, reduces the comfort and the moisture absorption of the fabric, is easy to yellow, is sensitive to high pH value, high temperature and the like, and is easy to generate oil stains and the like.

CN 102911365A discloses a preparation method of modified block polyether amino silicone oil, which improves the defect of poor hydrophilicity of common amino silicone oil and claims to be capable of transplanting yellowing, but the preparation method does not give any experimental data capable of proving the technical effect in the examples.

The Liaoning Colon fine chemical industry Co., Ltd discloses synthesis and performance research of amino polyether modified silicone oil (daily chemical science, No. 1, page 28-30 in 2017, synthesis and performance research of amino polyether modified silicone oil), which takes N-beta- (aminoethyl) -gamma-guanamine propyl methyl dimethoxy silane and epoxy polyether (alcohol terminated) as raw materials to synthesize amino polyether; the amino polyether modified cassia oil is synthesized by taking amino polyether and octamethylcyclotetrasiloxane as raw materials, and the prepared amino polyether modified silicone oil has good water absorption, but is unstable under alkaline conditions.

Therefore, on the basis of improving the water absorption of the amino silicone oil, how to improve the stability of the amino silicone oil is a problem to be solved by the technical personnel in the field and is a precondition for commercialization of the product.

Disclosure of Invention

1. The invention aims to provide a novel method.

The invention provides a preparation method of modified amino silicone oil with stable performance, which screens the type of epoxy terminated polyether, and replaces epoxy polyether (alcohol terminated) with monoallyl terminated polyoxyethylene polyoxypropylene epoxy ether (AEPH), so that the prepared amino silicone oil not only can obtain excellent water absorption, but also is stable under acid-base conditions, and has commercial prospect.

2. The technical scheme adopted by the invention is disclosed.

A preparation method of modified amino silicone oil with stable performance is characterized in that monoallyl end-capped polyoxyethylene polyoxypropylene epoxy ether and a silane coupling agent are used as raw materials to prepare amino polyether, and then the amino polyether and octamethylcyclotetrasiloxane (D4) are used as raw materials to prepare the modified amino silicone oil with stable performance.

Preferably, the preparation method specifically comprises the following steps:

1) synthesis of aminopolyethers

Reacting mono allyl terminated polyoxyethylene polyoxypropylene epoxy ether with silane coupling agent N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane in alcohol solvent, and removing the alcohol solvent by reduced pressure distillation after the reaction is finished to obtain amino polyether:

2) synthesis of modified amino silicone oil

The amino polyether and octamethylcyclotetrasiloxane generate modified amino silicone oil under the catalytic action of inorganic base at 60-90 ℃.

Preferably, the molar ratio of the monoallyl-terminated polyoxyethylene polyoxypropylene epoxy ether in the step 1) to the N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane is 1: 1;

preferably, the step 1) further comprises a step of purifying the aminopolyether, specifically, the aminopolyether is added into n-heptane, standing and layering are carried out, an upper layer is discarded, and a lower layer is the purified aminopolyether.

Preferably, the dosage of the aminopolyether in the step 2) is 5 to 10 percent of the weight of the octamethylcyclotetrasiloxane.

Preferably, the step 2) further comprises a purification step of the modified amino silicone oil, specifically, dichloromethane is adopted to dissolve the modified amino silicone oil, then anhydrous methanol is dripped, after the anhydrous methanol is added, white floccule is generated at the lower layer of the mixed solution, the upper layer solution is removed, and after 3 times of repetition, methanol and dichloromethane in the white floccule are distilled to obtain the purified modified amino silicone oil.

3. The technical effect produced by the invention.

(1) The invention adopts mono-allyl terminated polyoxyethylene polyoxypropylene epoxy ether and silane coupling agent as raw materials to prepare amino polyether for the first time, and then the amino polyether and octamethylcyclotetrasiloxane (D4) are used as raw materials to prepare the modified amino silicone oil which is stable under acid-base conditions.

(2) The modified amino silicone oil prepared by the invention has excellent water absorption, and the water absorption is 0.3 s.

Detailed Description

Examples of monoallyl-capped polyoxyethylenepolyoxypropylene epoxy ethers (AEPH) n (EO)/n (PO) 2/3, molar mass 1000 g/mol, from Duville trade, Hangzhou.

Example 1

1) Synthesis of amino polyether:

reacting monoallyl end-capped polyoxyethylene polyoxypropylene epoxy ether with equal molar weight and silane coupling agent N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane in an isopropanol solvent, and removing isopropanol by reduced pressure distillation after the reaction is finished to obtain amino polyether; adding the aminopolyether into n-heptane, standing, layering, removing the upper layer, and obtaining the lower layer which is the purified aminopolyether.

2) Synthesis of modified amino silicone oil

0.05g of purified aminopolyether reacts with 10g of octamethylcyclotetrasiloxane under the catalysis of 0.1g of sodium hydroxide at the temperature of 60-90 ℃ for 6-8h to generate the modified amino silicone oil. Dissolving the modified amino silicone oil by using dichloromethane, then dropwise adding anhydrous methanol, generating white floccule at the lower layer of the mixed solution after adding the anhydrous methanol, removing the upper layer solution, repeating for 3 times, and distilling the methanol and the dichloromethane in the white floccule to obtain the purified modified amino silicone oil.

Example 2

1) Synthesis of amino polyether:

reacting monoallyl end capping polyoxyethylene polyoxypropylene epoxy ether with equal molar weight and silane coupling agent N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane in methanol solvent, and removing methanol by reduced pressure distillation after the reaction is finished to obtain amino polyether; adding the aminopolyether into n-heptane, standing, layering, removing the upper layer, and obtaining the lower layer which is the purified aminopolyether.

2) Synthesis of modified amino silicone oil

0.08g of purified aminopolyether reacts with 10g of octamethylcyclotetrasiloxane under the catalytic action of 0.2g of sodium hydroxide at the temperature of 60-90 ℃ for 6-8h to generate the modified amino silicone oil. Dissolving the modified amino silicone oil by using dichloromethane, then dropwise adding anhydrous methanol, generating white floccule at the lower layer of the mixed solution after adding the anhydrous methanol, removing the upper layer solution, repeating for 3 times, and distilling the methanol and the dichloromethane in the white floccule to obtain the purified modified amino silicone oil.

Comparative example 1

Compared with the example 2, the preparation method adopts amino polyether 10 (containing 10C-C-O structures and terminated by methanol structure, and is from Liaoning Cologong), and other raw materials and preparation methods are the same as the example 2.

And (3) product performance detection: the acid stability and water absorption of the purified modified amino silicone oils of example 2 and comparative example 1 were tested by the methods of the prior art (daily chemical science, No. 1, No. 28 to No. 30, 2017, synthesis and performance research of amino polyether modified silicone oil), and the results show that the modified amino silicone oil prepared in example 2 of the present invention is in an emulsion state under acid (pH 5-6), alkali (pH 7.5-8.5) and neutral conditions, while the modified amino silicone oil in comparative example 1 is in an oil floating state under both alkaline and neutral conditions. The fabric absorbency measured in example 2 was 0.3/s, much higher than 0.5/s in comparative example 1.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.