阅读说明：本技术 聚醚多元醇及其制备方法和应用 (Polyether polyol and preparation method and application thereof ) 是由 宰少波 金晖 张志华 于 2019-10-22 设计创作，主要内容包括：本发明公开一种聚醚多元醇及其制备方法和应用,主要解决现有技术聚氨酯慢回弹泡沫开孔剂成本高或者开孔性较差的问题。通过采用一种聚醚多元醇,具有式(I)所示结构通式：R-[X-(AO)-m-(BO)-n-(SO)-k-H]-a,式(I)；其中,R-1为碳原子数1～100的脂肪基、芳香基、碳氧基、羰基、羧基、酯基、酰胺基或氢；AO为氧化乙烷或氧化丙烷,BO为氧化丁烷,SO为氧化苯乙烷,所述AO、BO、SO为任意顺序均聚、无规共聚、嵌段共聚组合的技术方案,较好地解决了该问题,可用于聚氨酯慢回弹泡沫材料的工业生产中。(The invention discloses polyether polyol and a preparation method and application thereof, and mainly solves the problems of high cost or poor opening property of a polyurethane slow-rebound foam opening agent in the prior art. By using a polyether polyol having the general structural formula shown in formula (I): r- [ X- (AO) m ‑(BO) n ‑(SO) k ‑H] a Formula (I); wherein R is 1 An aliphatic group, an aromatic group, a carbon-oxygen group, a carbonyl group, a carboxyl group, an ester group, an amide group or hydrogen, wherein the number of carbon atoms is 1-100; AO is ethylene oxide or propylene oxide, BO is butylene oxide, SO is styrene oxide, AO, BO, SO are the homopolymerization of arbitrary order, random copolymerization, block copolymerization combined technical scheme, have solved this problem well, can be used in the industrial production of the slow rebound foam material of polyurethane.)

1. A polyether polyol having the general structural formula shown in formula (I):

R-[X-(AO)_m-(BO)_n-(SO)_k-H]_aformula (I);

wherein R is₁One or more than two of aliphatic group, aromatic group, carbon oxygen group, carbonyl group, carboxyl group, ester group, amide group, polyether group, polyester group, polyamide group or hydrogen with 1-100 carbon atoms; AO is ethylene oxide or propylene oxide, BO is butylene oxide, SO is styrene oxide, and AO, BO and SO are the combination of homopolymerization, random copolymerization and block copolymerization in any sequence; x is O or N; m is more than or equal to 0 and less than or equal to 100, n is more than or equal to 1 and less than or equal to 100, and k is more than or equal to 1 and less than or equal to 50; a is the functionality, and a is more than or equal to 1 and less than or equal to 8.

2. Polyether polyol according to claim 1, characterized in that R is₁Is one or more than two of straight chain or branched chain alkane with 1-100 carbon atoms, olefin, aromatic hydrocarbon, polyether, polyester, polyamide or hydrogen.

3. A method of preparing a polyether polyol comprising the steps of:

in the presence of an alkali metal catalyst, the initiator R₁-[XH]_aRing-opening polymerization with epoxy compound to obtain polymer R₁-[X-(AO)_m-(BO)_n-(SO)_k-H]_a。

Wherein R is₁One or more than two of aliphatic group, aromatic group, carbon oxygen group, carbonyl group, carboxyl group, ester group, amide group, polyether group, polyester group, polyamide group or hydrogen with 1-100 carbon atoms; AO is ethylene oxide or propylene oxide, BO is butylene oxide, SO is styrene oxide, and AO, BO and SO are the combination of homopolymerization, random copolymerization and block copolymerization in any sequence; x is O or N; m is more than or equal to 0 and less than or equal to 100, n is more than or equal to 1 and less than or equal to 100, and k is more than or equal to 1 and less than or equal to 50; a is the functionality, and a is more than or equal to 1 and less than or equal to 8.

4. Process for the preparation of a polyether polyol according to claim 3, characterized in that R₁Is straight chain or branched chain alkane, olefin, aromatic hydrocarbon, polyether, polyester, polyamide with 1-100 carbon atoms, copolymer thereof or hydrogen.

5. A process for the preparation of polyether polyols according to claim 3, characterized in that: the alkali metal catalyst is one or more of alkali metal, alkali metal hydroxide, alkali metal alcoholate and alkali metal oxide; further preferably: the dosage of the alkali metal catalyst is 0.01-5% of the total mass of the initiator and the epoxy compound.

6. A process for the preparation of polyether polyols according to claim 3, characterized in that: the initiator is at least one of water, alcohols with 1-20 carbon atoms, polyhydroxy alcohols with 2-20 carbon atoms and 2-8 hydroxyl groups, saccharides or derivatives thereof, polyether polyol with 2-8 end groups, 1-8 hydroxyl groups on the end groups and 200-10000 in number average molecular weight, polyamine with 2-20 carbon atoms and 2-3 primary or secondary amino groups, and cyclic polyamine with 4-10 carbon atoms and 2-3 secondary amino groups.

7. A process for the preparation of polyether polyols according to claim 3, characterized in that: the amount of the initiator is 0.5-95% of the total mass of the initiator and the epoxy compound.

8. A process for the preparation of polyether polyols according to claim 3, characterized in that: the ring-opening polymerization reaction temperature is 60-180 ℃, and the reaction pressure is 0.001-1.0 MPa.

9. A process for the preparation of polyether polyols according to claim 3, characterized in that: after the ring-opening polymer reacts, optionally adding acid for neutralization, then adding an adsorbent for adsorption, dehydrating at high temperature and filtering; wherein the added acid is one or more of phosphoric acid, hydrochloric acid, sulfuric acid, formic acid, acetic acid and propionic acid, and the molar ratio of the added acid to the alkali metal catalyst is 0.1-1.1; the added adsorbent is one or more of magnesium silicate, aluminum silicate, magnesium aluminum silicate, activated carbon and diatomite; further preferably, the temperature of the high-temperature dehydration is preferably 80 to 110 ℃, and more preferably, the dehydration is accompanied by vacuum pumping or nitrogen bubbling.

10. Use of a polyether polyol as claimed in any one of claims 1 to 2.

Technical Field

The invention relates to polyether polyol and a preparation method and application thereof, in particular to polyether polyol containing phenylethane oxide and a preparation method and application thereof.

Background

Slow rebound polyurethane foam, also known as viscoelastic polyurethane foam, memory foam or energy absorbing foam. General soft foam polyurethane foam can recover rapidly due to the elasticity of the soft foam polyurethane foam after being acted by external force, the recovery time of slow rebound polyurethane foam can reach more than 3s, and the rebound time can be adjusted according to specific requirements. The foam has excellent special properties of buffering, sound insulation and the like, and can be applied to anti-seismic and buffering materials of aerospace, aviation, automobiles and the like and engine noise suppression. In recent years, the slow rebound pillow is widely used in high-grade cars as a seat cushion and a headrest and in home as a high-grade slow rebound pillow and a mattress.

The principle of the slow rebound foam is mainly the restraining effect, namely the slow rebound foam can restrain the rebound in the rebound process and make the rebound become slow. It is currently believed that this is due to the degree of phase separation of the polyurethane system and its particular glass transition temperature. Slow rebound polyethers are a mixture of polyethers having a wide variety of relative molecular mass distributions. At present, the domestic market adopts two categories: the hydroxyl value of one type is larger than 200mgKOH/g and even up to 260-270 mgKOH/g, and the hydroxyl value of the other type is smaller than 170mgKOH/g, so that the catalyst has higher activity and higher relative molecular weight. The use of POP polyether or no POP polyether improves the low-temperature performance. The flexibility and fatigue resistance of the foam can be improved by matching polyether with higher relative molecular mass and high activity with isocyanate with higher index.

The slow rebound foam has relatively low molecular weight, and more short branched chain structures exist in the molecules. This results in cell walls formed by reaction with isocyanate which are harder to break by gas than cell walls formed by reaction with higher molecular weight polyethers, so that the articles generally have significantly closed cells and shrink significantly. Therefore, a cell opener must be added when producing the slow rebound polyurethane foam. At present, the domestic pore-forming agent has high price and general pore-forming performance.

Disclosure of Invention

One of the technical problems to be solved by the invention is to provide the phenylethane-containing polyether polyol which can be used as a cell opening agent for polyurethane slow-resilience foam, can increase the cell opening performance of the foam, prevent cell closing, improve the foam structure and enable products to have lower shrinkage and better comfort.

The second technical problem to be solved by the present invention is to provide a method for preparing polyether polyol containing phenylethane oxide, which corresponds to the first technical problem.

The present invention is also directed to a method for producing a polyether polyol containing styrene oxide, which comprises the step of adding a polyether polyol containing styrene oxide to a polyether polyol containing styrene oxide.

In order to solve one of the technical problems, the invention adopts the following technical scheme: a polyether polyol containing oxidized phenylethane has a general structural formula shown in formula (I):

R₁-[X-(AO)_m-(BO)_n-(SO)_k-H]_aformula (I);

wherein R is₁One or more than two of aliphatic group, aromatic group, carbon oxygen group, carbonyl group, carboxyl group, ester group, amide group, polyether group, polyester group, polyamide group or hydrogen with 1-100 carbon atoms; AO is ethylene oxide or propylene oxide, BO is butylene oxide, SO is styrene oxide, and AO, BO and SO are the combination of homopolymerization, random copolymerization and block copolymerization in any sequence; x is O or N; m is more than or equal to 0 and less than or equal to 100, n is more than or equal to 1 and less than or equal to 100, and k is more than or equal to 1 and less than or equal to 50; a is the functionality, and a is more than or equal to 1 and less than or equal to 8.

In the above technical scheme, R₁Preferably one or more of linear or branched alkanes having 1 to 100 carbon atoms, olefins, aromatic hydrocarbons, polyether groups, polyester groups, polyamide groups, and hydrogen.

In order to solve the second technical problem, the invention adopts the technical scheme that: a preparation method of polyether polyol containing phenylethane oxide comprises the following steps:

in the presence of an alkali metal catalyst, the initiator R₁-[XH]_aRing-opening polymerization with epoxy compound to obtain polymer R₁-[X-(AO)_m-(BO)_n-(SO)_k-H]_aThe epoxy compound is ethylene oxide, propylene oxide, butylene oxide and styrene oxide;

wherein R is₁One or more than two of aliphatic group, aromatic group, carbon oxygen group, carbonyl group, carboxyl group, ester group, amide group, polyether group, polyester group, polyamide group or hydrogen with 1-100 carbon atoms; AO is ethylene oxide or propylene oxide, BO is butylene oxide, SO is styrene oxide, and AO, BO and SO are homopolymerization, random copolymerization and block copolymerization in any orderA combination of block copolymerizations; x is O or N; m is more than or equal to 0 and less than or equal to 100, n is more than or equal to 1 and less than or equal to 100, and k is more than or equal to 1 and less than or equal to 50; a is the functionality, and a is more than or equal to 1 and less than or equal to 8.

In the above technical scheme, R₁Preferably one or more of linear or branched alkanes having 1 to 100 carbon atoms, olefins, aromatic hydrocarbons, polyether groups, polyester groups, polyamide groups, and hydrogen.

In the above technical solution, the alkali metal catalyst is preferably one or more of alkali metal, alkali metal hydroxide, alkali metal alcoholate and alkali metal oxide; more preferably one or more of potassium hydroxide, sodium hydroxide, cesium hydroxide, potassium methoxide, potassium tert-butoxide, metallic potassium, metallic sodium, etc., and most preferably potassium hydroxide or potassium methoxide.

In the technical scheme, the dosage of the alkali metal catalyst is preferably 0.01-5% of the total mass of the initiator and the epoxy compound, and more preferably 0.1-0.5%

In the above technical scheme, the initiator is a compound containing active hydrogen atoms and is selected from water or an organic compound having a partial structural formula of-OH or-NH-.

First, the active hydride is water. The organic compound having a partial structural formula-OH includes, for example, carboxylic acids having 1 to 20 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, lauric acid and the like; polycarboxylic acids having 2 to 20 carbon atoms and 2 to 6 carboxylic acids, such as oxalic acid, malonic acid, succinic acid, maleic acid terephthalic acid, etc.; alcohols having 1 to 20 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, isoamyl alcohol, etc.; polyhydric alcohols having 2 to 20 carbon atoms and 2 to 8 hydroxyl groups, such as ethylene glycol, propylene glycol, glycerin, diglycerin, butylene glycol, pentaerythritol, and the like; saccharides or derivatives thereof, such as glucose, sorbitol, fructose, sucrose, bisphenol A, and the like.

Organic compounds having a partial structure of-NH-as the active hydrogen compound include, for example, primary aliphatic or aromatic amines having 1 to 20 carbon atoms, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, benzylamine, aniline, etc.; secondary aliphatic or aromatic amines having 2 to 20 carbon atoms, such as diethylamine, methylethylamine, di-n-propylamine, diphenylamine and the like; polyamines having 2 to 20 carbon atoms and having 2 to 3 primary or secondary amino groups, such as ethylenediamine, hexamethylenediamine, melamine, N, N' -dimethylethyleneamine, etc.; unsaturated cyclic secondary amines having 4 to 20 carbon atoms, such as 3-pyrroline, pyrrole, indole, carbazole, imidazole, pyrazole, purine, etc.; cyclic polyamines having 4 to 20 carbon atoms and having 2 to 3 secondary amine groups, such as pyrazine, piperazine, etc.; substituted or N-monosubstituted acid amides having 2-20 carbon atoms, such as acetamide, propionamide, N-methylpropionamide, 2-pyrrolidone, etc.; and imides of dicarboxylic acids having 4 to 10 carbon atoms, such as succinimide, maleimide, etc.

Among these active hydrogen compounds, preferred are compounds having a partial structural formula of-OH including, for example, polyhydric alcohols having 2 to 20 carbon atoms and having 2 to 8 hydroxyl groups, such as ethylene glycol, propylene glycol, 1-4 butylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, etc.; saccharides or derivatives thereof, such as glucose, sorbitol, fructose, sucrose, etc.

Other active hydrides useful in the present invention include polymers having terminal active hydrogen atoms such as polyethers, polyesters, polyamides, and copolymers thereof.

In the above technical scheme, the amount of the initiator is preferably 0.5 to 95% of the total mass of the initiator and the epoxy compound, and more preferably 2 to 50%.

In the technical scheme, the amount of AO is 0-95% of the total mass of the initiator and the epoxy compound, the amount of BO is 5-100% of the total mass of the initiator and the epoxy compound, and the amount of SO is 1-20% of the total mass of the initiator and the epoxy compound.

In the above technical scheme, in the ring-opening polymerization reaction, the reaction temperature is preferably 60 to 180 ℃, and more preferably 90 to 120 ℃.

In the above technical scheme, in the ring-opening polymerization reaction, the reaction pressure is preferably 0.001 to 1.0MPa, and more preferably 0.01 to 0.3 MPa.

In the technical scheme, after the ring-opening polymer reacts, the method optionally comprises the steps of adding acid for neutralization, then adding an adsorbent for adsorption, dehydrating at high temperature and filtering; wherein, the added acid is preferably one or more of phosphoric acid, hydrochloric acid, sulfuric acid, formic acid, acetic acid and propionic acid, preferably phosphoric acid and hydrochloric acid, and more preferably phosphoric acid. The molar mass ratio of the added acid to the alkali metal catalyst is 0.9-1.1; the added adsorbent is one or more of magnesium silicate, aluminum silicate, magnesium aluminum silicate, active carbon and diatomite, preferably magnesium silicate and aluminum silicate; the high-temperature dehydration temperature is preferably 80-110 ℃, and the vacuum pumping or nitrogen bubbling can be performed.

In the process of the present invention, a solvent may also be used, if necessary. The solvent used includes, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane and the like; aromatic hydrocarbons such as benzene, toluene, etc.; ethers such as diethyl ether, tetrahydrofuran, anisole and the like; aprotic solvents such as dimethylsulfoxide, N, N-dimethylformamide and the like. In addition to these, any solvent can be used as long as it does not inhibit the polymerization reaction of the process of the present invention. When a solvent is used in the polymerization reaction, the polymer produced by the process of the present invention may be used as a cell opener for polyurethane foam by removing the solvent. However, it is also possible to use the above-mentioned raw materials or surfactants by treating them with mineral acids such as hydrochloric acid, phosphoric acid and sulfuric acid, organic carboxylic acids such as formic acid, acetic acid and propionic acid, carbon dioxide or acidic ion exchange resins. Further, the purification may be carried out by a conventional purification such as washing with water, an organic solvent or a mixture thereof.

The polymerization reaction in the process of the present invention can also be carried out in the presence of an inert gas such as nitrogen, argon, etc., as required.

In order to solve the third technical problem, the invention adopts the technical scheme that: the application of polyether polyol containing phenylethane oxide is provided.

In the above technical solution, the application is not limited, for example, but not limited to, the cell opening agent is used as a cell opening agent for slow rebound polyurethane foam, and the problem of high cost or poor cell opening property of the slow rebound polyurethane foam in the prior art can be solved.

The invention obtains the structure R by introducing styrene oxide-containing ethane into a polymer chain₁-[X-(AO)_m-(BO)_n-(SO)_k-H]_aThe polyether glycol is used as a cell opening agent for polyurethane slow-resilience foam, and has the advantages of good cell opening property, closed cell prevention, foam structure improvement, low shrinkage rate and good comfort of products.

By adopting the technical scheme of the invention, the obtained polyether polyol containing the styrene oxide is used as the cell opening agent for the slow rebound foam of polyurethane, has the advantages of better cell opening property, prevention of cell closing, improvement of foam structure, lower shrinkage rate of products and better comfort, has the shrinkage rate equivalent to that of foreign products, is better than that of domestic cell opening agents, and obtains better technical effect.

The present invention will be described in more detail with reference to examples, but the present invention is not to be construed as being limited to the examples.

Detailed Description

[ example 1 ]

60g of glycerol, KOH4g, was placed in a 3L autoclave equipped with pressure and temperature gauges, a stirrer, and feed inlet. After nitrogen displacement, the temperature was raised to 100 ℃ and vacuum dehydration was carried out. Then the temperature was raised to 115 ℃ and 300g of ethylene oxide, then 1800g of butylene oxide and then 240g of styrene oxide were added. After completion of the reaction, the low boiling point fraction in the system was extracted by a vacuum pump, phosphoric acid and water were added, stirring was carried out for 30min, and then 4.2g of aluminum silicate was added, vacuum dehydration was carried out, and the adsorbent was filtered to obtain 2380g of a polymer having no odor. According to the coacervation permeation chromatography using polystyrene as a standard, the number average molecular weight was 4200 and the molecular weight distribution was 1.21.

[ example 2 ]

The procedure is as in example 1, except that 700g of a 2:1 mixture of propylene oxide and ethylene oxide are used instead of 300g of ethylene oxide. As a result, 2770g of a polymer was obtained. According to the coacervation permeation chromatography using polystyrene as a standard, the number average molecular weight was 5000 and the molecular weight distribution was 1.15.

[ example 3 ]

The procedure of example 1 was followed except that 76g of 1, 2-propanediol was used instead of 60g of glycerol. As a result, 2370g of a polymer was obtained. According to coacervation permeation chromatography using polystyrene as standard, the number average molecular weight is 3100 and the molecular weight distribution is 1.15.

[ example 4 ]

The procedure is as in example 1, except that 250g of a 3-functional polyether polyol having a number average molecular weight of 500 are used instead of 60g of glycerol. As a result, 2560g of a polymer was obtained. According to the coacervation permeation chromatography using polystyrene as a standard, the number average molecular weight was 6100 and the molecular weight distribution was 1.20.

[ example 5 ]

Following the procedure in example 1 except that ethylene oxide was not added, the amount of butylene oxide was changed to 2000g, 2280g of a polymer was obtained. According to the coacervation permeation chromatography using polystyrene as a standard, the number average molecular weight was 4200 and the molecular weight distribution was 1.17.

The cell opening agent A prepared in the embodiment 4 of the invention is selected and added into the same slow rebound formulation according to different fractions, polyurethane slow rebound foam products are prepared in the same die, and the cell opening effect is compared, as shown in Table 1.

TABLE 1 tapping Effect of different addition parts of tapping agent A in the same Slow rebound formulation

	Without adding	Adding 1 part of	Adding 2 parts of
				Quality of sample	400	400	400
Shrinkage rate at 24 hours%	8％	5	2.7

It can be seen that the shrinkage of the slow recovery foam decreases after the cell opener A is used.