阅读说明：本技术 一种用于皮革润湿剂的丁醇聚醚多元醇的制备方法 (Preparation method of butanol polyether polyol for leather wetting agent ) 是由 贾飞 孙言丛 耿佃勇 于 2020-11-27 设计创作，主要内容包括：本发明属于化工合成技术领域,具体涉及一种用于皮革润湿剂的丁醇聚醚多元醇的制备方法,以叔丁醇或异丁醇为起始剂,以碱金属或有机胺为催化剂,与环氧烷烃进行聚合反应,制得用于皮革润湿剂的丁醇聚醚多元醇。本发明制备工艺简单,制得的聚醚多元醇具有粘度低、表面张力低、润湿速度快、乳化能力强等特点。(The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of butanol polyether polyol for a leather wetting agent. The preparation process is simple, and the prepared polyether polyol has the characteristics of low viscosity, low surface tension, high wetting speed, strong emulsifying capacity and the like.)

1. A preparation method of butanol polyether polyol used as a leather wetting agent is characterized by comprising the following steps: tert-butyl alcohol or isobutyl alcohol is used as an initiator, alkali metal or organic amine is used as a catalyst, and the tert-butyl alcohol or isobutyl alcohol and alkylene oxide are subjected to polymerization reaction to prepare the butyl alcohol polyether polyol used as the leather wetting agent.

2. The method for preparing butanol polyether polyol for leather wetting agent according to claim 1, wherein the method comprises the following steps:

adding an initiator and a catalyst into a reaction kettle, performing nitrogen replacement, measuring the oxygen content in the kettle to be less than 10-300ppm, vacuumizing to the pressure of-0.1 to-0.06 MPa, heating to 40-90 ℃, stirring for 1-3h, then starting to add alkylene oxide, keeping the temperature in the kettle at 80-160 ℃, keeping the pressure at 0-0.5MPa stable, continuously dropwise adding the alkylene oxide, keeping the temperature in the kettle at 80-140 ℃, keeping the pressure at 0-0.4MPa, after the feeding is finished, performing internal pressure reaction for 2-4h, and removing the incompletely reacted alkylene oxide in vacuum to obtain the butanol polyether polyol used as the leather wetting agent; wherein the mass ratio of the initiator to the alkylene oxide is 5-15: 85-95; the dosage of the catalyst is 0.05-1% of the total mass of the system.

3. The method for preparing butanol polyether polyol as claimed in claim 1 or 2, wherein the alkali metal is one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium methoxide or potassium methoxide.

4. The method for preparing butanol polyether polyol as claimed in claim 1 or 2, wherein the organic amine is one or more of dimethylamine, trimethylamine, ethylenediamine or cyclohexylamine.

5. The method for preparing the butanol polyether polyol as the leather wetting agent according to claim 1 or 2, wherein the alkylene oxide is one or more of ethylene oxide, propylene oxide or butylene oxide.

6. The method for preparing butanol polyether polyol as claimed in claim 2, wherein the oxygen content in the kettle measured after nitrogen substitution is less than 50-150 ppm.

7. The method for preparing the butanol polyether polyol as the leather wetting agent according to claim 2, wherein the vacuum is pumped to a pressure of-0.095 to-0.085 Mpa.

Technical Field

The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of butanol polyether polyol for a leather wetting agent.

Background

The leather industry covers the main industries of leather making, shoes making, leather clothing, leather pieces, fur, products thereof and the like, and the matching industries of leather chemical industry, leather hardware, leather machinery, auxiliary materials and the like. The association degree of the upstream and the downstream is high, the product is very green depending on market pulling, and the characteristics of earning foreign exchange, enriching people and employment are integrated. The total demand of the global leather is about 1.0 hundred million square meters, which is equivalent to the yield of 3 hundred million cowhide (standard leather), and the yield of the Chinese leather is reduced to about 7000 million standard leather, which accounts for about 23.33 percent of the yield of the global leather.

The wetting agent has the effects of enhancing the adhesive force, and enabling water to permeate into the surface of an article by reducing the surface tension so as to achieve the wetting function. Wetting agents can also improve hiding power, tinting strength. Improve the hand feeling of the coating film and beautify the surface coating. The wetting agent is particularly applied to aqueous wood paint, color paste, aqueous industrial coating, aqueous ink and the like. The traditional butanol polyether wetting agent mainly comprises n-butanol, and has slightly poor performances such as wetting speed, emulsifying capacity and the like.

Disclosure of Invention

The invention aims to provide a preparation method of butanol polyether polyol used as a leather wetting agent, which has the characteristics of simple preparation process, low viscosity, low surface tension, high wetting speed, strong emulsifying capacity and the like.

The invention relates to a preparation method of butanol polyether polyol used as a leather wetting agent, which is characterized by comprising the following steps: tert-butyl alcohol or isobutyl alcohol is used as an initiator, alkali metal or organic amine is used as a catalyst, and the tert-butyl alcohol or isobutyl alcohol and alkylene oxide are subjected to polymerization reaction to prepare the butyl alcohol polyether polyol used as the leather wetting agent.

Further, the method comprises the following steps:

adding an initiator and a catalyst into a reaction kettle, performing nitrogen replacement, measuring the oxygen content in the kettle to be less than 10-300ppm, vacuumizing to the pressure of-0.1 to-0.06 MPa, heating to 40-90 ℃, stirring for 1-3h, then starting to add alkylene oxide, keeping the temperature in the kettle to be 80-160 ℃, keeping the pressure to be 0-0.5MPa stable, continuously dropwise adding the alkylene oxide, keeping the temperature in the kettle to be 80-140 ℃, preferably 105-115 ℃, and the pressure to be 0-0.4MPa, after the feeding is finished, performing internal pressure reaction for 2-4h, and removing the incompletely reacted alkylene oxide in vacuum to obtain the butanol polyether polyol for the leather wetting agent; wherein the mass ratio of the initiator to the alkylene oxide is 5-15: 85-95; the dosage of the catalyst is 0.05-1%, preferably 0.1-0.5% of the total mass of the system.

Further, the alkali metal is one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium methoxide or potassium methoxide.

Furthermore, the organic amine is one or more of dimethylamine, trimethylamine, ethylenediamine or cyclohexylamine.

Furthermore, the alkylene oxide is one or more of Ethylene Oxide (EO), Propylene Oxide (PO) or Butylene Oxide (BO). Propylene Oxide (PO) and Butylene Oxide (BO), Butylene Oxide (BO) and Ethylene Oxide (EO) are preferred.

Furthermore, the oxygen content in the kettle is measured to be less than 50-150ppm after nitrogen replacement.

Furthermore, the vacuum is pumped to the pressure of-0.095 to-0.085 MPa.

Compared with the prior art, the invention has the following beneficial effects: the preparation method is scientific, reasonable, simple and feasible, can reduce the generation of waste water and waste residue in the refining process of the crude polyether, and is economic and environment-friendly; the prepared butanol polyether polyol has the characteristics of multiple types, good wettability, small surface tension, strong emulsifying capacity, wide application range and the like.

Detailed Description

The present invention will be further described with reference to the following examples.

All the starting materials used in the examples are commercially available, except where otherwise indicated.

Comparative example 1:

a method for preparing butanol polyether polyol as wetting agent for leather includes such steps as adding n-butanol (300 g) and sodium methoxide (4.9 g) to a 5L high-pressure reactor with stirrer, metering device, heating temp controller, cooler and pressure sensor, nitrogen displacement, measuring the oxygen content in reactor to less than 100ppm, vacuumizing to-0.09 MPa, heating to 100 ℃, stirring for 2h, starting to add 50g of a mixture of propylene oxide alkane (PO) and Ethylene Oxide (EO), keeping the temperature in the kettle at 100 +/-2 ℃ and the pressure at 0.3MPa, adding 1857g of a mixture of Propylene Oxide (PO) and Ethylene Oxide (EO) (mass ratio PO/EO is 1/1) when the pressure is reduced to 0, keeping the temperature in the kettle at 110 +/-5 ℃ and the pressure at 0.4MPa, reacting under internal pressure for 4h after feeding is finished, removing the unreacted alkylene oxide monomer in vacuum, and carrying out post-treatment and refining to obtain the butanol polyether polyol used as the leather wetting agent.

The analytical indexes are as follows: a hydroxyl value of 105mgKOH/g, a viscosity of 20 mPas/25 ℃, a pH value of 5.5 and 3ppm of sodium ions.

Comparative example 2:

a preparation method of butanol polyether polyol used for leather wetting agent comprises the steps of adding 300g of n-butanol and 4.9g of potassium hydroxide into a 5L high-pressure kettle which is provided with a stirrer, a meter, a heating temperature control device, a cooling device and a pressure sensor, carrying out nitrogen replacement, measuring the oxygen content in the kettle to be less than 100ppm, vacuumizing to-0.09 MPa, heating to 100 ℃, stirring for 2 hours, starting to add 50g of propylene oxide, keeping the temperature in the kettle at 100 +/-2 ℃ and the pressure at 0.3MPa, adding 900g of Propylene Oxide (PO) when the pressure is reduced to 0, keeping the temperature in the kettle at 110 +/-5 ℃ and the pressure at 0.4MPa, and carrying out internal pressure reaction for 4 hours after feeding is finished; pressurizing to 0.05MPa, adding 950g of Ethylene Oxide (EO), reacting for 4 hours under internal pressure after feeding, removing the alkylene oxide monomer which is not completely reacted in vacuum, and obtaining the butanol polyether glycol used for the leather wetting agent after post-treatment and refining.

The analytical indexes are as follows: a hydroxyl value of 101mgKOH/g, a viscosity of 25 mPas/25 ℃, a pH value of 6.25 and 2ppm of potassium ions.

Example 1:

a method for preparing butanol polyether glycol used for leather wetting agent, add 300g tertiary butanol, 8.55g ethylenediamine in 5L autoclave equipped with agitator, counter, heating temperature control device, cooling device and pressure sensor, carry on the nitrogen substitution, after measuring the oxygen content in the kettle is less than 100ppm, vacuumize to-0.09 MPa, raise the temperature to 60 duC and stir for 2 hours, begin to add 50g epoxybutane (BO) and Epoxyethane (EO) mixture (mass ratio BO/EO equals 1/1), keep the temperature in the kettle 80 + -2 deg.C, pressure 0.3MPa, until the pressure drops to 0, add epoxybutane (BO) and Epoxyethane (EO) mixture (mass ratio BO/EO equals 1/1)2500g, keep the temperature in the kettle 85 + -5 deg.C, pressure 0.4MPa, after the feed finishes, the internal pressure reacts for 4 hours, remove the epoxy alkane monomer that has not reacted completely in vacuum, and after post-treatment and refining, the butanol polyether glycol used as the leather wetting agent can be obtained.

The analytical indexes are as follows: a hydroxyl value of 80mgKOH/g, a viscosity of 35mPa · s/25 ℃ and a pH value of 7.2.

Example 2:

a method for preparing butanol polyether glycol used for leather wetting agent, add 300g isobutanol, 6g potassium hydroxide in 5L autoclave equipped with agitator, counter, heating temperature control device, cooling device and pressure sensor, carry on the nitrogen substitution, after measuring the oxygen content in the kettle and is less than 100ppm, vacuumize to-0.09 MPa, raise the temperature to 70 duC and stir 2h, begin to add 50g epoxypropane (PO) and epoxybutane (BO) (PO/BO (mass ratio) is 1/1), keep the temperature in the kettle 90 + -2 duC, the pressure is 0.3MPa, after the pressure drops to 0, add epoxypropane (PO) and epoxybutane (BO) (PO/BO (mass ratio) is 1/1) the mixture 1500g, keep the temperature in the kettle 95-105 duC, the pressure is 0.4MPa, after the feeding finishes, the internal pressure reacts for 4 hours; pressurizing to 0.05MPa, adding 1500g of Ethylene Oxide (EO), reacting for 4 hours under internal pressure after feeding, removing the alkylene oxide monomer which is not completely reacted in vacuum, and obtaining the butanol polyether glycol used for the leather wetting agent after post-treatment and refining.

The analytical indexes are as follows: a hydroxyl value of 65mgKOH/g, a viscosity of 50 mPas/25 ℃, a pH value of 6.5 and 1ppm of potassium ions.

Test example:

comparative example 1-comparative example 2, example 1-example 2 surface properties of different polyether structures Butanol polyethers are shown in the following Table:

the invention enriches the product line and enables customers to select proper products according to the requirements.