阅读说明：本技术 高承载阻燃型海绵用聚醚多元醇及其制备方法 (Polyether polyol for high-load flame-retardant sponge and preparation method thereof ) 是由 周玉波 孙露霞 孙兆任 公维英 王文涛 于 2019-09-27 设计创作，主要内容包括：本发明涉及聚醚多元醇技术领域,具体涉及一种高承载阻燃型海绵用聚醚多元醇及其制备方法。所述的高承载阻燃型海绵用聚醚多元醇,是以3官低聚物聚醚多元醇和三(2-羟乙基)异氰脲酸酯为复合起始剂,以双金属氰化络合物为催化剂,与环氧丙烷和环氧乙烷开环聚合制得；3官低聚物聚醚多元醇是以甘油为起始剂,与环氧丙烷开环聚合制备的低聚物聚醚多元醇,分子量为500。本发明的高承载阻燃型海绵用聚醚多元醇,不仅提高了海绵的承载性、降低了制品密度,还具备优异的阻燃性能；本发明同时提供了科学合理、简单易行的制备方法。(The invention relates to the technical field of polyether polyol, and particularly relates to polyether polyol for a high-load-bearing flame-retardant sponge and a preparation method thereof. The polyether polyol for the high-load flame-retardant sponge is prepared by ring-opening polymerization of 3-functional oligomer polyether polyol and tris (2-hydroxyethyl) isocyanurate serving as composite initiators and a bimetallic cyanide complex serving as a catalyst with propylene oxide and ethylene oxide; the 3-functional oligomer polyether polyol is oligomer polyether polyol prepared by ring-opening polymerization of glycerin as an initiator and propylene oxide, and has a molecular weight of 500. The polyether polyol for the high-load-bearing flame-retardant sponge not only improves the load bearing property of the sponge and reduces the density of products, but also has excellent flame-retardant property; the invention also provides a scientific, reasonable, simple and feasible preparation method.)

1. The utility model provides a high polyether polyol for bearing fire-retardant sponge which characterized in that: the compound is prepared by taking 3-functional oligomer polyether polyol and tris (2-hydroxyethyl) isocyanurate as a compound initiator and taking a double metal cyanide complex as a catalyst to carry out ring-opening polymerization with propylene oxide and ethylene oxide;

wherein the molar ratio of the 3-functional oligomeric polyether polyol to the tris (2-hydroxyethyl) isocyanurate is from 1:4 to 4: 1.

2. The polyether polyol for high load-bearing flame-retardant sponge according to claim 1, wherein: the 3-functional oligomer polyether polyol is oligomer polyether polyol prepared by ring-opening polymerization of glycerin as an initiator and propylene oxide, and has a molecular weight of 500.

3. The polyether polyol for high load-bearing flame-retardant sponge according to claim 1, wherein: the amount of the double metal cyanide complex catalyst is 0.002-0.01% of the sum of the mass of the 3-functional oligomer polyether polyol, the mass of the tris (2-hydroxyethyl) isocyanurate, the mass of the propylene oxide and the mass of the ethylene oxide.

4. The polyether polyol for high load-bearing flame-retardant sponge according to claim 1, wherein: the amount of ethylene oxide used is 5-10% of the sum of the mass of the 3-functional oligomer polyether polyol, tris (2-hydroxyethyl) isocyanurate, propylene oxide and ethylene oxide.

5. The polyether polyol for high load-bearing flame-retardant sponge according to claim 1, wherein: the amount of propylene oxide used is 68.3 to 81.4% of the sum of the masses of the 3-functional oligomer polyether polyol, tris (2-hydroxyethyl) isocyanurate, propylene oxide and ethylene oxide.

6. The polyether polyol for high load-bearing flame-retardant sponge according to claim 1, wherein: the hydroxyl value of the polyether polyol for the low-density high-bearing sponge is 54.5-57.5 mgKOH/g.

7. The preparation method of the polyether polyol for the high-load flame-retardant sponge according to any one of claims 1 to 6, characterized by comprising the following steps:

(1) adding 3-functional oligomer polyether polyol, tris (2-hydroxyethyl) isocyanurate and a bimetallic cyanide complex catalyst into a high-pressure reaction kettle, heating to 110-130 ℃, performing vacuum dehydration, and then adding part of propylene oxide to perform an induction activation reaction;

(2) and when the pressure in the reaction kettle continuously decreases and decreases to negative pressure and the temperature continuously increases, indicating that the polymerization reaction starts, continuously adding propylene oxide and ethylene oxide for polymerization reaction, after the feeding is finished, continuously carrying out aging reaction for 0.5-1h, then vacuumizing for 1-2h to remove the monomer, cooling and discharging to obtain the high-load-bearing flame-retardant type polyether polyol for the sponge.

8. The preparation method of the polyether polyol for the high-load-bearing flame-retardant sponge according to claim 7, characterized in that: the mass of the propylene oxide added in the step (1) is 5-15% of the sum of the mass of the polyether polyol of the 3-functional oligomer and the mass of the tris (2-hydroxyethyl) isocyanurate.

9. The preparation method of the polyether polyol for the high-load-bearing flame-retardant sponge according to claim 7, characterized in that: the temperature of the induced activation reaction in the step (1) is 128-132 ℃, and the reaction pressure is less than or equal to 0.2 MPa.

10. The preparation method of the polyether polyol for the high-load-bearing flame-retardant sponge according to claim 7, characterized in that: the polymerization temperature in the step (2) is 130-145 ℃.

Technical Field

The invention relates to the technical field of polyether polyol, and particularly relates to polyether polyol for a high-load-bearing flame-retardant sponge and a preparation method thereof.

Background

The polyurethane soft foam plastic is called soft foam for short, commonly called sponge, is soft polyurethane foam plastic with certain elasticity, is mainly used for furniture cushion materials, vehicle seat cushion materials and various soft liner laminated composite materials, and has wide application range.

Sponge, a porous organic polymer, has a strong combustibility, and the lower the density, the stronger the combustibility, which is in great contradiction with the trend of low density in the sponge market. The traditional method for improving the flame retardant property of the sponge is to add a flame retardant mixture formed by combining halogen-containing polymer or halogen-containing flame retardant in the formula, but the added flame retardant can reduce the mechanical property of the sponge product; with time, the flame retardant may migrate and precipitate from the product, affecting stability and flame retardancy. Another method for improving the flame retardance is to introduce flame retarding elements and groups into the molecular structure, but the mechanical properties of the sponge are lost, and the density of the sponge product is limited.

Patent CN2017113147898 discloses a synergistic flame-retardant sponge, which improves flame-retardant performance of a sponge product and reduces influence of flame retardant on various physical properties of the sponge product by adjusting a formula and a synergistic effect generated by different proportions of various flame retardants. However, the method still adds flame retardant and has the same disadvantages.

Patent CN 2017110158176 discloses a preparation method of phosphorus-containing flame-retardant polyether polyol, which uses a traditional KOH alkali metal catalysis process, and has the disadvantages of complicated steps, long reaction period, great difficulty in industrial production, only one flame-retardant element and limited flame-retardant effect.

Patent CN201610844390X discloses a low-density high-load-bearing sponge and a manufacturing process thereof, which prepares the low-density high-load-bearing sponge by optimizing a formula and a production process, and does not consider the effect of polyether polyol.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide the polyether polyol for the high-load-bearing flame-retardant sponge, which not only improves the load bearing property of the sponge and reduces the density of products, but also has excellent flame-retardant property; the invention also provides a scientific, reasonable, simple and feasible preparation method.

The polyether polyol for the high-load flame-retardant sponge is prepared by ring-opening polymerization of 3-functional oligomer polyether polyol and tris (2-hydroxyethyl) isocyanurate serving as composite initiators and a bimetallic cyanide complex serving as a catalyst with propylene oxide and ethylene oxide.

The 3-functional oligomer polyether polyol is oligomer polyether polyol prepared by ring-opening polymerization of glycerin as an initiator and propylene oxide, has a molecular weight of 500, is a commercially available product and has a brand number of 305 or MN 500.

Tris (2-hydroxyethyl) isocyanurate, also known as cek, the english name 1,3,5-Tris (2-hydroxyethenyl) cyanuric acid, EINECS No.: 212-660-9, formula C₉H₁₆N₃O₆And is a commercial product.

The molar ratio of the 3-functional oligomer polyether polyol to the tris (2-hydroxyethyl) isocyanurate is from 1:4 to 4: 1.

The double metal cyanide complex catalyst is a commercial product and is used in an amount of 0.002-0.01% of the sum of the mass of the 3-functional oligomer polyether polyol, tris (2-hydroxyethyl) isocyanurate, propylene oxide and ethylene oxide.

The amount of ethylene oxide used is 5-10% of the sum of the mass of the 3-functional oligomer polyether polyol, tris (2-hydroxyethyl) isocyanurate, propylene oxide and ethylene oxide.

The amount of propylene oxide used is 68.3 to 81.4% of the sum of the masses of the 3-functional oligomer polyether polyol, tris (2-hydroxyethyl) isocyanurate, propylene oxide and ethylene oxide.

The polyether polyol for the low-density high-bearing sponge has the functionality of 3 and the hydroxyl value of 54.5-57.5 mgKOH/g.

The preparation method of the polyether polyol for the high-load flame-retardant sponge comprises the following steps:

(1) adding 3-functional oligomer polyether polyol, tris (2-hydroxyethyl) isocyanurate and a bimetallic cyanide complex catalyst into a high-pressure reaction kettle, heating to 110-130 ℃, performing vacuum dehydration, and then adding part of propylene oxide to perform an induction activation reaction;

(2) and when the pressure in the reaction kettle continuously decreases and decreases to negative pressure and the temperature continuously increases, indicating that the polymerization reaction starts, continuously adding propylene oxide and ethylene oxide for polymerization reaction, after the feeding is finished, continuously carrying out aging reaction for 0.5-1h, then vacuumizing for 1-2h to remove the monomer, cooling and discharging to obtain the high-load-bearing flame-retardant type polyether polyol for the sponge.

The mass of the propylene oxide added in the step (1) is 5-15% of the sum of the mass of the polyether polyol of the 3-functional oligomer and the mass of the tris (2-hydroxyethyl) isocyanurate.

The temperature of the induced activation reaction in the step (1) is 128-132 ℃, and the reaction pressure is less than or equal to 0.2 MPa.

The polymerization temperature in the step (2) is 130-145 ℃.

Preferably, the preparation method of the polyether polyol for the high-load flame-retardant sponge comprises the following steps:

(1) adding 3-functional oligomer polyether polyol, tris (2-hydroxyethyl) isocyanurate and a bimetallic cyanide complex catalyst into a high-pressure reaction kettle, heating to 110-130 ℃, keeping the vacuum degree lower than-0.093 MPa, vacuumizing and dehydrating for 0.5-2h, then adding propylene oxide accounting for 5-15% of the mass sum of the 3-functional oligomer polyether polyol and the tris (2-hydroxyethyl) isocyanurate for induction activation reaction, wherein the induction temperature is 128-132 ℃, and the induction pressure is less than or equal to 0.2 MPa;

(2) and when the pressure in the reaction kettle continuously decreases and decreases to negative pressure and the temperature continuously increases, indicating that the polymerization reaction starts, continuously adding epoxypropane and epoxyethane for polymerization reaction, wherein the reaction temperature is 130-145 ℃, after the addition is finished, continuously carrying out aging reaction for 0.5-1h, then vacuumizing for 1-2h to remove the monomer, cooling and discharging to obtain the high-load flame-retardant polyether polyol for the sponge.

Compared with the prior art, the invention has the following beneficial effects:

(1) according to the invention, the special initiator tris (2-hydroxyethyl) isocyanurate is added on the basis of the conventional initiator 3-functional oligomer polyether polyol, and the initiator contains an isocyanurate structure, so that the flame retardance is excellent, and meanwhile, the bearing property of the product can be improved;

(2) the equivalent weight of the polyether polyol provided by the invention is consistent with that of the polyether polyol for the traditional sponge, and when the sponge is prepared by using the polyether polyol provided by the invention, the proportion of the polyether polyol provided by the invention is determined according to the performance requirements, so that the sponge is flexible and convenient;

(3) the invention solves the defects of small contact area and difficult reaction of the solid particle initiator tris (2-hydroxyethyl) isocyanurate by selecting proper initiator proportion; the polyether polyol is prepared by a bimetallic catalysis process, the catalysis efficiency is high, three wastes are not generated, and the production cost is low.

Detailed Description

The present invention is further illustrated by the following examples, but the scope of the present invention is not limited thereto, and modifications of the technical solutions of the present invention by those skilled in the art should be within the scope of the present invention.