阅读说明：本技术 一种聚醚多元醇及其制备方法与应用 (Polyether polyol and preparation method and application thereof ) 是由 宰少波 金晖 张志华 于 2020-07-01 设计创作，主要内容包括：本发明公开了一种聚醚多元醇及其制备方法与应用,所述聚醚多元醇中含有C-(2)～C-(4)的氧化烷基和C-(5)～C-(6)的氧化烷基结构单元,所述C-(2)～C-(4)的氧化烷基选自氧化乙基、氧化丙基和氧化丁基中的至少一种,所述C-(5)～C-(6)的氧化烷基选自氧化戊基、氧化环戊基、氧化己基、氧化环己基中的至少一种。所述聚醚多元醇如下制备：在催化剂存在下,起始剂与环氧化合物进行开环聚合反应,任选地进行封端处理,经后处理得到所述聚醚多元醇。本发明所述聚醚多元醇可以用作聚氨酯慢回弹泡沫用开孔剂,具有开孔性好、防止闭孔、改善泡沫结构、使制品具有较低的收缩率和较好的舒适感的优点,收缩率与国外产品相当,好于国产开孔剂,取得了较好的技术效果。(The invention discloses polyether polyol and a preparation method and application thereof, wherein the polyether polyol contains C 2 ～C 4 Alkyl oxide of and C 5 ～C 6 C said 2 ～C 4 Is selected from at least one of oxyethylene, oxypropyl and oxybutyl, C 5 ～C 6 The alkyl oxide(s) is (are) at least one selected from the group consisting of an amyl oxide, a cyclopentyl oxide, a hexyl oxide, and a cyclohexyl oxide. The polyether polyol is prepared as follows: in the presence of a catalyst, an initiator and an epoxy compound are subjected to ring-opening polymerization reaction, optionally subjected to end-capping treatment, and subjected to post-treatment to obtain the polyether polyol. The polyether polyol can be used as a cell opening agent for polyurethane slow-resilience foam, has good cell opening property and prevents the closingThe foam has the advantages of improving the foam structure, enabling the product to have lower shrinkage rate and better comfort, the shrinkage rate is equivalent to that of foreign products, the product is better than that of a domestic cell opening agent, and better technical effect is achieved.)

1. A polyether polyol containing C₂～C₄And C is an oxyalkylene structural unit₅～C₆C said₂～C₄Is selected from at least one of oxyethylene, oxypropyl and oxybutyl, C₅～C₆The alkyl oxide(s) is (are) at least one selected from the group consisting of an amyl oxide, a cyclopentyl oxide, a hexyl oxide, and a cyclohexyl oxide.

2. Polyether polyol according to claim 1, wherein C is₂～C₄Is selected from oxyethylene and/or oxypropyl and oxybutane, C₅～C₆The alkyl oxide(s) of (b) is (are) at least one selected from the group consisting of hexyl oxide and cyclohexyl oxide, for example cyclohexyl oxide.

3. Polyether polyol according to claim 1 or 2, wherein the polyether polyol has the structure according to formula (I):

R₁-[X-(AO)_m-(BO)_n-(CO)_k-R₂]_aformula (I);

in the formula (I), R₁Is selected from C₁～C₁₀₀Fatty group of (C)₆～C₁₀₀Aryl of (A), C₁～C₁₀₀Carbonyl of (a), or hydrogen; and/or, X is O or NR ', R' is selected from H, alkyl or aryl; and/or, R₂Selected from hydrogen, C₁～C₂₀Fatty group of (C)₆～C₂₀Or- (C ═ O) R₃Wherein R is₃Selected from hydrogen, C₁～C₂₀Fatty radical or C of₆～C₂₀An aromatic group of (a); and/or, AO represents an oxyethylene group and/or an oxypropyl group, BO represents an oxybutyl group, and CO represents said C₅～C₆The AO, BO and CO are combined by homopolymerization, random copolymerization and block copolymerization in any sequence; 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; and/or a represents the functionality of the initiator, 1. ltoreq. a.ltoreq.8.

4. Polyether polyol according to claim 3, wherein in formula (I), R₁Is selected from C₁～C₂₀Fatty group of (C)₆～C₂₀Aryl of (A), C₁～C₂₀Carbonyl or hydrogen of (a); and/or, R' is selected from H, C₁～C₂₀Alkyl or C₆～C₂₀An aromatic group of (a); and/or, R₂Selected from hydrogen, C₁～C₁₀Fatty group of (C)₆～C₁₀Or- (C ═ O) R₃Wherein R is₃Selected from hydrogen, C₁～C₁₀Fatty radical or C of₆～C₁₀An aromatic group; and/or m is more than or equal to 0 and less than or equal to 95, n is more than or equal to 5 and less than or equal to 100, and k is more than or equal to 1 and less than or equal to 20; and/or a is more than or equal to 2 and less than or equal to 8.

5. A process for preparing the polyether polyol of any one of claims 1 to 4, comprising: in the presence of a catalyst, an initiator reacts with an epoxy compound, and then the polyether polyol is obtained through optional end capping treatment and post treatment.

6. The production method according to claim 5, characterized in that a protective gas replacement treatment and a dehydration treatment are performed after the addition of the catalyst; preferably, the protective atmosphere is selected from inert atmosphere and/or nitrogen; more preferably, after the catalyst is added, nitrogen replacement treatment is performed, and the temperature is raised to 70-100 ℃ for vacuum dehydration treatment.

7. Preparation process according to claim 5, characterized in that the catalyst is chosen from alkali metal catalysts and/or DMC catalysts, preferably,

the alkali metal catalyst is selected from at least one of alkali metal, alkali metal hydroxide, alkali metal alcoholate and alkali metal oxide, preferably at least one selected from potassium hydroxide, sodium hydroxide, cesium hydroxide, potassium methoxide, potassium tert-butoxide, potassium metal, sodium metal and the like, and more preferably selected from potassium hydroxide and/or potassium methoxide; and/or

The DMC catalyst has a structural formula as shown in formula (II):

M¹ _a[M² _d(CN)_f].M¹ _b[M³ _e(CN)_g].M¹ _cX_h.Y_i.Z_j.kH₂o formula (II)

In formula (II):

M¹、M³selected from Zn, Fe, Ni, Mn, Co, Sn, Ph, Mo, Al, V, Sr, W, Cu or Cr; wherein M is¹Preferred embodiments of (a) are Zn, Ni or Co; m³Is Zn or Fe;

M²selected from Fe, Co, Cr, Mn, Ir, Ni, Rh, Ru or V, and the preferable scheme is Fe or Co;

x is selected from halogen element and OH^-、NO₃ ^-、CO₃ ^2-、SO₄ ^2-Or ClO₃ ^2-；

Y is selected from C having a tertiary alcohol structure₄～C₁₀Organic alcohol, its preferred embodiment is tert-butyl alcohol or tert-amyl alcohol;

z is selected from aliphatic ester, aromatic monoester or aromatic diester, the preferable embodiment is aromatic diester, and the more preferable embodiment is phthalate;

a. b and c represent M¹The number of ions of (a); d. e each represents M²、M³The number of ions; f. g represents the ion number of CN; h. i, j and k represent X, Y, Z and H, respectively₂The number of O.

8. The production method according to claim 7,

when the alkali metal catalyst is adopted, the dosage of the alkali metal catalyst is 0.01 to 5 percent of the total mass of the initiator and the epoxy compound, and the preferred dosage is 0.1 to 0.5 percent;

when DMC catalysts are used, they are used in amounts of from 0.001% to 5%, preferably from 0.003% to 0.01%, based on the total mass of starter and epoxy compound.

9. The method according to claim 5, wherein the initiator is a substance containing active hydrogen atoms, preferably a copolymer of at least two species selected from the group consisting of a compound containing at least one of a terminal amine group, a terminal hydroxyl group and a terminal carboxyl group, a polyalkylene oxide, a polyether, a polylactide, a polycarbonate, a polyamide and a polyether-polyester-polyamide, preferably a compound containing at least one of a terminal amine group, a terminal hydroxyl group and a terminal carboxyl group, more preferably a compound containing a terminal hydroxyl group;

preferably, when the blocking treatment is not performed, the initiator is selected from a compound containing at least one of a terminal amine group, a terminal hydroxyl group and a terminal carboxyl group, and when the blocking treatment is performed, the initiator is selected from a compound containing a terminal hydroxyl group and/or a terminal carboxyl group.

10. The method of claim 9, wherein the initiator is R₁-(X’)_aX' is selected from carboxyl, hydroxyl or amine, preferably, the initiator is selected from water and C₁～C₂₀Monocarboxylic acid compound of (2), C₂～C₂₀Polycarboxylic acid compound of (1), C₁～C₂₀Monohydroxyalcohol compound of (2), C₂～C₂₀A polyhydroxy alcohol compound, a saccharide compound or saccharide derivative containing a polyhydroxy group, a molecular weight of 200 to 1000 containing 1 to 8 terminal hydroxyl groups0g/mol of a polyether polyol, C₁～C₂₀Esters of (5) and (C)₆～C₂₀Aromatic primary amine, C₂～C₂₀Esters of (5) and (C)₆～C₂₀Of a secondary aromatic amine, C₂～C₂₀Saturated alkyl polyamine compound of (1), C₄～C₁₀Unsaturated cyclic polyamine compound of (1), C₂～C₂₀Substituted or N-monosubstituted acid amides of (A) or (B), C₄～C₁₀At least one of dicarboxylic acid imides of (1), preferably from C₂～C₂₀A polyhydric alcohol compound of (a);

more preferably, C is₁～C₂₀Is selected from at least one of formic acid, acetic acid, propionic acid, butyric acid and lauric acid, and/or, C₂～C₂₀The polycarboxylic acid compound of (A) is at least one selected from oxalic acid, malonic acid, succinic acid, maleic acid and terephthalic acid, and/or, C₁～C₂₀The monohydric alcohol compound is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and isoamylol, and/or C₂～C₂₀The polyhydroxy alcohol compound is at least one selected from ethylene glycol, propylene glycol, glycerol, trihydroxymethyl propane, dipentaerythritol, diglycerol, butanediol and pentaerythritol, and/or the carbohydrate compound or carbohydrate derivative containing polyhydroxy is at least one selected from glucose, sorbitol, fructose, sucrose and bisphenol A, and/or the C₁～C₂₀Esters of (5) and (C)₆～C₂₀Is selected from at least one of methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, benzylamine, aniline, and/or C₂～C₂₀Esters of (5) and (C)₆～C₂₀Is selected from at least one of diethylamine, methylethylamine, di-n-propylamine, diphenylamine, and/or, C₂～C₂₀Is selected from at least one of ethylenediamine, hexamethylenediamine, melamine, N' -dimethylethyleneamine, and/or, C₄～C₁₀Unsaturated cyclic poly(s)The amine compound is at least one selected from 3-pyrroline, pyrrole, indole, carbazole, imidazole, pyrazole, purine, pyrazine and piperazine, and/or C₂～C₂₀Is selected from at least one of acetamide, propionamide, N-methylpropionamide, 2-pyrrolidone, and/or, the C₄～C₁₀The dicarboxylic acid imide of (a) is selected from succinimide and/or maleimide;

more preferably, the initiator is at least one selected from the group consisting of ethylene glycol, propylene glycol, 1-4 butanediol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, glucose, sorbitol sugar, fructose, sucrose.

11. The process according to claim 5, wherein the amount of the initiator is 0.5 to 95%, preferably 2 to 50% of the total amount of the initiator and the epoxy compound.

12. The method according to claim 5, wherein the epoxy compound is selected from C₂～C₄Epoxy compound of (2) and C₅～C₆An epoxy compound of (a); preferably, said C₂～C₄Is selected from at least one of ethylene oxide, propylene oxide and butylene oxide, C₅～C₆The epoxy compound is at least one of cyclopentane epoxide, cyclohexane epoxide and cyclohexane epoxide; more preferably, C is₂～C₄The epoxy compound of (a) is selected from ethylene oxide and/or propylene oxide and butylene oxide; said C is₅～C₆The epoxy compound of (2) is at least one selected from the group consisting of cyclohexene oxide and cyclohexene oxide.

13. The process according to claim 12, wherein the ethylene oxide and/or propylene oxide is reacted with butylene oxide, C₅～C₆The molar ratio of the epoxy compound (b) is (0-100): (1-100): 1-50), preferably (0-95): 5-100): 1-20.

14. The production method according to claim 5, wherein the end-capping treatment is carried out using an end-capping agent,

removing unreacted initiator and epoxy compound in a reaction system before end-capping treatment, preferably removing at 80-110 ℃, and more preferably removing at 80-110 ℃ under vacuum or nitrogen bubbling; and/or

The end-capping agent is R₂-J, wherein R₂Selected from hydrogen, C₁～C₂₀Fatty group of (C)₆～C₂₀Or- (C ═ O) R₃，R₃Selected from hydrogen, C₁～C₂₀Fatty radical or C of₆～C₂₀An aromatic group; j is selected from halogen, hydroxy or acyl; preferably, the capping agent is selected from at least one of halogenated hydrocarbons, organic acids, compounds containing anhydride groups and compounds containing acid halide groups; more preferably, the blocking agent is selected from at least one of methyl iodide, ethyl iodide, propyl iodide, ethylene iodide, toluene iodide, acetic acid, acetic anhydride, acetyl chloride, benzoyl chloride; and/or

The molar use ratio of the end-capping reagent to the initiator is (1-1.3): 1, preferably (1.02-1.2): 1.

15. The production method according to any one of claims 5 to 14, wherein the ring-opening polymerization reaction is carried out under the conditions: the reaction temperature is 60-180 ℃, and the reaction pressure is 0.001-1.0 MPa; preferably, when an alkali metal catalyst is employed, the conditions of the ring-opening polymerization reaction are: the reaction temperature is 90-120 ℃, and the reaction pressure is 0.01-0.3 MPa; when DMC catalysts are used, the conditions for the ring-opening polymerization are: the reaction temperature is 110-150 ℃, and the reaction pressure is 0.01-0.3 MPa.

16. The method of claim 15,

when an alkali metal catalyst is used, the post-treatment is carried out as follows: vacuumizing treatment, acid neutralization treatment, adsorption treatment, dehydration treatment and filtration, preferably, washing with water and/or an organic solvent optionally after filtration;

when a DMC catalyst is used, the post-treatment comprises an evacuation treatment, preferably optionally adsorption treatment and filtration before the evacuation treatment.

17. Polyether polyol obtained by the preparation method of any one of claims 5 to 16.

18. Use of the polyether polyol according to any one of claims 1 to 4 or the polyether polyol obtained by the production method according to any one of claims 5 to 16 in a cell opening agent for a polyurethane slow rebound foam.

Technical Field

The invention belongs to the field of polyether polyol, and particularly relates to polyether polyol capable of being used as a polyurethane cell opening agent.

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

In order to overcome the problems in the prior art, the inventors have conducted extensive studies to find that C is incorporated into polyether polyol₅～C₆May be made of an oxyalkylene structural unitThe opening rate of the polyurethane foam is improved, and therefore, the polyether polyol which can be used as a polyurethane opening agent is provided. The polyether polyol can be used as a cell opening agent for polyurethane slow-resilience foam, can increase the cell opening performance of the foam, prevent closed cells, improve the foam structure and enable products to have lower shrinkage rate and better comfort.

It is an object of the present invention to provide polyether polyols which contain C₂～C₄And C is an oxyalkylene structural unit₅～C₆Wherein said C is₂～C₄Is selected from at least one of oxyethylene, oxypropyl and oxybutyl, C₅～C₆The alkyl oxide(s) is (are) at least one selected from the group consisting of an amyl oxide, a cyclopentyl oxide, a hexyl oxide, and a cyclohexyl oxide.

Wherein the pentyl group in the oxidized pentyl group is a chain structure and does not include a cyclopentyl group, and the hexyl group in the oxidized hexyl group is a chain structure and does not include a cyclohexyl group.

The inventor finds that C is introduced into polyether polyol through a large amount of experiments₅～C₆Of (2) (especially by introduction of C)₆～C₆Alkyl oxide) can improve the lipophilicity of the polyurethane foam, and the opening effect of the polyurethane foam is better.

In a preferred embodiment, said C₂～C₄Comprises oxyethylene and/or oxypropylene groups and oxybutane groups, said C₅～C₆The alkyl oxide(s) of (b) is (are) at least one selected from the group consisting of hexyl oxide and cyclohexyl oxide, for example cyclohexyl oxide.

In a preferred embodiment, the polyether polyol has the structure according to formula (I):

R₁-[X-(AO)_m-(BO)_n-(CO)_k-R₂]_aformula (I);

wherein, in formula (I), R₁Is selected from C₁～C₁₀₀Fatty group of (C)₆～C₁₀₀Aryl of (A), C₁～C₁₀₀Carbonyl or hydrogen of (a); and/or, X is O or NR ', R' is selected from H, alkyl or aryl; and/or, R₂Selected from hydrogen, C₁～C₂₀Fatty group of (C)₆～C₂₀Or- (C ═ O) R₃Wherein R is₃Selected from hydrogen, C₁～C₂₀Fatty radical or C of₆～C₂₀An aromatic group; and/or, AO represents an oxyethylene group and/or an oxypropyl group, BO represents an oxybutyl group, and CO represents said C₅～C₆The AO, BO and CO are combined by homopolymerization, random copolymerization and block copolymerization in any sequence; 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; and/or a represents the functionality of the initiator, 1. ltoreq. a.ltoreq.8.

In a further preferred embodiment, in formula (I), R₁Is selected from C₁～C₂₀Fatty group of (C)₆～C₂₀Aryl of (A), C₁～C₂₀Carbonyl or hydrogen of (a); and/or, R₂Selected from hydrogen, C₁～C₁₀Fatty group of (C)₆～C₂₀Or- (C ═ O) R₃Wherein R is₃Selected from hydrogen, C₁～C₁₀Fatty radical or C of₆～C₁₀An aromatic group; and/or m is more than or equal to 0 and less than or equal to 95, n is more than or equal to 5 and less than or equal to 100, and k is more than or equal to 1 and less than or equal to 20; and/or a is more than or equal to 2 and less than or equal to 8.

It is a second object of the present invention to provide a process for the preparation of a polyether polyol according to the first object of the present invention, which comprises: in the presence of a catalyst, an initiator reacts with an epoxy compound, and then is subjected to end capping treatment optionally and post-treatment to obtain the polyether polyol R₁-[X-(AO)_m-(BO)_n-(CO)_k-R₂]_aAnd (4) showing.

In a preferred embodiment, the protective gas replacement treatment and the dehydration treatment are carried out after the addition of the catalyst.

Wherein the protective atmosphere is selected from an inert atmosphere and/or nitrogen.

In a more preferred embodiment, after the catalyst is added, nitrogen substitution treatment is performed, and the temperature is raised to 70 to 100 ℃ to perform vacuum dehydration treatment.

Wherein, the method of the invention needs to be carried out under anhydrous and anaerobic conditions.

In a preferred embodiment, the catalyst is selected from alkali metal catalysts and/or DMC catalysts.

In a further preferred embodiment, the alkali metal catalyst is selected from at least one of alkali metals, alkali metal hydroxides, alkali metal alcoholates, and alkali metal oxides, preferably from at least one of potassium hydroxide, sodium hydroxide, cesium hydroxide, potassium methoxide, potassium tert-butoxide, potassium metal, sodium metal, and the like, and more preferably from potassium hydroxide and/or potassium methoxide.

In a still further preferred embodiment, the DMC catalyst is selected from any DMC catalyst disclosed in the prior art, preferably having a formula as shown in formula (II):

M¹ _a[M² _d(CN)_f].M¹ _b[M³ _e(CN)_g].M¹ _cX_h.Y_i.Z_j.kH₂o formula (II)

In the formula (II):

M¹、M³selected from Zn, Fe, Ni, Mn, Co, Sn, Ph, Mo, Al, V, Sr, W, Cu or Cr; wherein M is¹Preferred embodiments of (a) are Zn, Ni or Co; m³Is Zn or Fe;

M²selected from Fe, Co, Cr, Mn, Ir, Ni, Rh, Ru or V, and the preferable scheme is Fe or Co;

x is selected from halogen element and OH^-、NO₃ ^-、CO₃ ^2-、SO₄ ^2-Or ClO₃ ^2-；

Y is selected from C having a tertiary alcohol structure₄～C₁₀Organic alcohol, its preferred embodiment is tert-butyl alcohol or tert-amyl alcohol;

z is selected from aliphatic ester, aromatic monoester or aromatic diester, the preferable embodiment is aromatic diester, and the more preferable embodiment is phthalate;

a. b and c represent M¹The number of ions of (a); d. e each represents M²、M³The number of ions; f. g represents the ion number of CN; h. i, j and k represent X, Y, Z and H, respectively₂The number of O.

Among them, for the DMC catalyst represented by the formula (II), see the laid-open patent CN 110684187A. Also, the choice of the DMC catalyst is not limited to that given by formula (II) above, but may be selected from any other DMC catalyst disclosed in the prior art.

In a preferred embodiment, when an alkali metal catalyst is used, it is used in an amount of 0.01 to 5% by weight based on the total mass of the initiator and the epoxy compound; when DMC catalyst is used, its dosage is 0.001% -5% of total mass of initiator and epoxy compound.

In a further preferred embodiment, when an alkali metal catalyst is used, it is used in an amount of 0.1% to 0.5% of the total mass of the initiator and the epoxy compound; when DMC catalyst is used, its dosage is 0.003% -0.01% of total mass of initiator and epoxy compound.

Among these, DMC activity is higher than that of the alkali metal catalyst, so that the amount thereof is significantly lower than that of the alkali metal catalyst.

In the present invention, an alkali metal catalyst may be preferably used when the capping treatment is not performed, and a DMC catalyst may be preferably used when the capping treatment is performed.

In a preferred embodiment, the initiator is a substance containing active hydrogen atoms, preferably a copolymer of at least two of a compound containing at least one of a terminal amine group, a terminal hydroxyl group and a terminal carboxyl group, a polyalkylene oxide, a polyether, a polylactide, a polycarbonate, a polyamide, a polyether-polyester-polyamide, preferably a compound containing at least one of a terminal amine group, a terminal hydroxyl group and a terminal carboxyl group, more preferably a compound containing a terminal hydroxyl group.

Wherein, when the end capping treatment is not carried out, the initiator is selected from compounds containing at least one of terminal amine groups, terminal hydroxyl groups and terminal carboxyl groups, and when the end capping treatment is carried out, the initiator is selected from compounds containing terminal hydroxyl groups and/or terminal carboxyl groups. Among these, DMC catalysts are not capable of catalyzing amine-terminated starters.

In the present invention, the hydroxyl-terminated compound includes water. When the initiator is selected from polymers, polyether polyol, polyester polyol and polycarbonate with the molecular weight of 300-5000 are preferable.

In a further preferred embodiment, the initiator is R₁-(X’)_aX' is selected from carboxyl, hydroxyl or amine, preferably, the initiator is selected from water and C₁～C₂₀Monocarboxylic acid compound of (2), C₂～C₂₀Polycarboxylic acid compound of (1), C₁～C₂₀Monohydroxyalcohol compound of (2), C₂～C₂₀A polyol compound, a saccharide compound or saccharide derivative containing a polyol, a polyether polyol having a molecular weight of 200 to 10000g/mol and containing 1 to 8 terminal hydroxyl groups, and C₁～C₂₀Esters of (5) and (C)₆～C₂₀Of an aromatic primary amine, C₂～C₂₀Esters of (5) and (C)₆～C₂₀Aromatic secondary amine, C₂～C₂₀Saturated alkyl polyamine compound of (1), C₄～C₁₀Unsaturated cyclic polyamine compound of (1), C₂～C₂₀Substituted or N-monosubstituted acid amides of (A) or (B), C₄～C₁₀At least one of dicarboxylic acid imides of (1), preferably from C₂～C₂₀A polyhydric alcohol compound of (a).

In a still further preferred embodiment, said C₁～C₂₀The monocarboxylic acid compound of (A) is at least one selected from formic acid, acetic acid, propionic acid, butyric acid and lauric acid, and C is₂～C₂₀The polycarboxylic acid compound is at least one selected from oxalic acid, malonic acid, succinic acid and maleic acid terephthalic acid, and C is₁～C₂₀The monohydric alcohol compound is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and isoamylol, and the C is₂～C₂₀The polyhydroxy alcohol compound is at least one selected from ethylene glycol, propylene glycol, glycerol, trihydroxymethyl propane, dipentaerythritol, diglycerol, butanediol and pentaerythritol, and the saccharide compound or saccharide derivative containing polyhydroxy (such as 2-8 hydroxyl) is selected from glucose and sorbitolAt least one of sugar alcohol, fructose, sucrose and bisphenol A, and C₁～C₂₀Esters of (5) and (C)₆～C₂₀The aromatic primary amine of (A) is selected from at least one of methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, benzylamine and aniline, and C₂～C₂₀Esters of (5) and (C)₆～C₂₀The aromatic secondary amine is at least one selected from diethylamine, methylethylamine, di-n-propylamine and diphenylamine, and C is₂～C₂₀The saturated alkyl polyamine compound (preferably containing 2 to 3 primary or secondary amine groups) is at least one selected from the group consisting of ethylenediamine, hexamethylenediamine, melamine and N, N' -dimethylethyleneamine, and C₄～C₁₀The unsaturated cyclic polyamine compound (C) is at least one selected from the group consisting of 3-pyrroline, pyrrole, indole, carbazole, imidazole, pyrazole, purine, pyrazine and piperazine₂～C₂₀The substituted or N-monosubstituted acid amide is at least one of acetamide, propionamide, N-methylpropionamide and 2-pyrrolidone, and the C is₄～C₁₀The dicarboxylic acid imide of (a) is selected from succinimide and/or maleimide.

In a still further preferred embodiment, the initiator is selected from at least one of ethylene glycol, propylene glycol, 1-4 butanediol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, glucose, sorbitol sugar, fructose, sucrose.

In a preferred embodiment, the amount of the starter is from 0.5% to 95%, preferably from 2% to 50%, based on the total amount of starter and epoxy compound.

In a preferred embodiment, the epoxy compound is selected from C₂～C₄Epoxy compound of (2) and C₅～C₆An epoxy compound of (1).

In a further preferred embodiment, said C₂～C₄Is selected from at least one of ethylene oxide, propylene oxide and butylene oxide, C₅～C₆The epoxy compound is selected from the group consisting of cyclopentane epoxide, hexane epoxide and cyclohexane epoxideAt least one of hexane.

In a still further preferred embodiment, said C₂～C₄The epoxy compound of (a) is selected from ethylene oxide and/or propylene oxide and butylene oxide; said C is₅～C₆The epoxy compound of (2) is at least one selected from the group consisting of cyclohexene oxide and cyclohexene oxide, for example cyclohexene oxide.

The inventor finds that C is introduced in the preparation of polyether polyol through a large amount of experiments₅～C₆Of epoxy compounds, especially of C₆The epoxy compound can improve the lipophilicity of the product and has better effect on opening pores of polyurethane bubbles.

In a preferred embodiment, the ethylene oxide and/or propylene oxide is/are reacted with butylene oxide, C₅～C₆The molar ratio of the epoxy compound (b) is (0-100): (1-100): 1-50), preferably (0-95): 5-100): 1-20.

In a preferred embodiment, the conditions of the ring-opening polymerization reaction are: the reaction temperature is 60-180 ℃, and the reaction pressure is 0.001-1.0 MPa.

In a further preferred embodiment, when an alkali metal catalyst is employed, the conditions of the ring-opening polymerization reaction are: the reaction temperature is 90-120 ℃, and the reaction pressure is 0.01-0.3 MPa; when DMC catalysts are used, the conditions for the ring-opening polymerization are: the reaction temperature is 110-150 ℃, and the reaction pressure is 0.01-0.3 MPa.

In the present invention, the pressure means gauge pressure.

In the present invention, the end-capping treatment is not carried out when an alkali metal catalyst is used (because the post-treatment is very troublesome), and the end-capping treatment is carried out when a DMC catalyst is used.

In a preferred embodiment, if the blocking treatment is performed, unreacted initiator and epoxy compound in the reaction system are removed before the blocking treatment, and the removal treatment is preferably performed at 80 to 110 ℃, and more preferably at 80 to 110 ℃ under vacuum or under nitrogen bubbling.

In a preferred embodiment, the capping treatment is carried out by adding a capping agent and optionally a capping catalyst.

In a further preferred embodiment, the capping agent is R2-J, wherein R is₂Selected from hydrogen, C₁～C₂₀Fatty group of (C)₆～C₂₀Or- (C ═ O) R₃，R₃Selected from hydrogen, C₁～C₂₀Fatty radical or C of₆～C₂₀An aromatic group; j is selected from halogen, hydroxy or acyl; preferably, the capping agent is selected from at least one of halogenated hydrocarbons, organic acids, compounds containing anhydride groups and compounds containing acid halide groups; more preferably, the blocking agent is selected from at least one of methyl iodide, ethyl iodide, propyl iodide, ethylene iodide, toluene iodide, acetic acid, acetic anhydride, acetyl chloride, and benzoyl chloride.

In a further preferred embodiment, the molar ratio of the blocking agent to the initiator is (1 to 1.3):1, preferably (1.02 to 1.2): 1.

In the present invention, if the end-capping treatment is carried out, the end-capping catalyst is optional, and it is determined mainly by which end-capping agent is used, that is, by which end-capping reaction is used to determine whether or not the end-capping catalyst is used. Meanwhile, if the end-capping catalyst is used, the selection and the dosage of the end-capping catalyst can be selected according to the technical scheme disclosed in the prior art.

In a preferred embodiment, a solvent selected from at least one of aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, ethereal solvents and aprotic solvents is optionally added to the reaction system.

In a further preferred embodiment, the aliphatic hydrocarbon is selected from at least one of pentane, hexane, heptane, cyclohexane, the aromatic hydrocarbon solvent is selected from benzene and/or toluene, the ethereal solvent is selected from at least one of diethyl ether, tetrahydrofuran, anisole, and the aprotic solvent is selected from dimethylsulfoxide and/or N, N-dimethylformamide.

Among them, the selection of the solvent is not limited to the above, and may be selected from any other solvents as long as the solvent does not inhibit the polymerization reaction of the method of the present invention. Therefore, the present invention can perform bulk polymerization of the epoxy monomer, and can also perform solution polymerization by adding a solvent.

In a preferred embodiment, when an alkali metal catalyst is employed, the post-treatment is carried out as follows: vacuum treatment, acid neutralization treatment, adsorption treatment, dehydration treatment and filtration, preferably, washing with water and/or an organic solvent is optionally performed after filtration.

Wherein, the filtration and dehydration treatment can also be carried out. The vacuum pumping can remove low boiling point fractions in the system, such as unreacted epoxy monomers, unreacted starters and other small molecule byproducts, and the like, and the adsorbent is added to adsorb and remove the catalyst in the system.

In a preferred embodiment, in the post-treatment with the alkali metal catalyst, the acid neutralization treatment includes solution neutralization with addition of an acid, treatment with carbon dioxide, and treatment with an acidic ion exchange resin.

In a further preferred embodiment, the acid is selected from at least one of phosphoric acid, hydrochloric acid, sulfuric acid, formic acid, acetic acid, propionic acid, and preferably, the molar ratio of the added acid to the alkali metal catalyst is (0.1-1.1): 1.

Wherein, when the acid is inorganic acid, the acid solution is acid water solution, and when the acid is organic acid, the acid solution is acid organic solution.

In a preferred embodiment, when a DMC catalyst is used, the post-treatment comprises a vacuuming treatment, preferably optionally followed by an adsorption treatment and filtration.

In the case of using a DMC catalyst, the amount of the DMC catalyst used is small and remains in the polyether polyol with little effect on the later stage, so that the catalyst can be removed (for example, by adsorption) during the aftertreatment, or the low-boiling fraction can be removed by direct evacuation without the need for treatment.

In a preferred embodiment, an adsorbent selected from at least one of magnesium silicate, aluminum silicate, magnesium aluminum silicate, activated carbon, diatomaceous earth, preferably from magnesium silicate and/or aluminum silicate, is added for the adsorption treatment.

In a further preferred embodiment, the adsorbent is used in an amount of 0.01 to 10 wt%, more preferably 0.1 to 1 wt%.

In a preferred embodiment, the dehydration treatment is carried out at 80 to 110 ℃, preferably with evacuation or nitrogen bubbling.

It is a further object of the present invention to provide polyether polyols obtainable by the process for the preparation according to the second object of the present invention.

The fourth object of the present invention is to provide the use of the polyether polyol according to one or three of the objects of the present invention in a cell opener for a polyurethane slow recovery foam.

The polyether polyol can solve the problems of high cost or poor opening performance of the polyurethane slow-rebound foam opening agent in the prior art.

The invention is achieved by introducing C into the polymer chain₅～C₆To give an oxyalkylated structural unit of the structure R₁-[X-(AO)_m-(BO)_n-(CO)_k-R₂]_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.

Compared with the prior art, the invention has the following beneficial effects: by adopting the technical scheme of the invention, the obtained polyether polyol is used as a cell opening agent for polyurethane slow-resilience foam, 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.

Detailed Description

While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.

The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.

[ example 1 ]

60g of glycerol and 4g of KOH are added into a 3L pressure kettle provided with a pressure and temperature meter, a stirring device and a raw material inlet. After nitrogen displacement, the temperature was raised to 100 ℃ and vacuum dehydration was carried out. The temperature was then raised to 115 ℃ and 300g of ethylene oxide, then 1800g of butylene oxide and then 240g of cyclohexane oxide were added. After the reaction was completed, 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, then 4.2g of aluminum silicate was added, vacuum dehydration was carried out, and the adsorbent was filtered to obtain 2380g of polyether polyol having no odor. According to the coacervation permeation chromatography using polystyrene as a standard, the number average molecular weight was 4350 and the molecular weight distribution was 1.21.

[ example 2 ]

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 polyether polyol was obtained. According to the coacervation permeation chromatography using polystyrene as a standard, the number average molecular weight was 6000 and the molecular weight distribution was 1.22.

[ example 3 ]

100g of a 3-functional polyether polyol having a molecular weight of 500 and 0.06g of a DMC catalyst (described in the embodiment of patent publication CN 104927040A) were placed in a 3-liter autoclave equipped with a pressure gauge, a temperature gauge, a stirring device and a feed inlet for the starting materials. After nitrogen displacement, the temperature was raised to 100 ℃ and vacuum dehydration was carried out. The temperature was then raised to 130 ℃ and a 2:1 mixture of 700g of propylene oxide and ethylene oxide was added, followed by 1460g of butylene oxide and then 240g of cyclohexane oxide. After completion of the reaction, the low boiling fraction in the system was extracted by a vacuum pump to obtain a polyether polyol having a hydroxyl value of 14mg KOH/g.

[ example 4 ]

100g of polyether polyol having a molecular weight of 500 and 0.06g of DMC catalyst (see the embodiment of patent publication CN 104927040A) were placed in a 3L autoclave equipped with a pressure gauge, a temperature gauge, a stirring device and a feed inlet for the starting materials. After nitrogen displacement, the temperature was raised to 100 ℃ and vacuum dehydration was carried out. The temperature was then raised to 135 ℃ and a 2:1 mixture of 700g of propylene oxide and ethylene oxide was added, followed by 1460g of butylene oxide and then 240g of cyclohexane oxide. After completion of the reaction, the low boiling fraction in the system was extracted by a vacuum pump to obtain polyether having a hydroxyl value of 14mg KOH/g. Then adding 25g of acetic anhydride, stirring and reacting for 3 hours at 130 ℃ and normal pressure, and then removing unreacted acetic anhydride and micromolecule by-products in vacuum to obtain polyether polyol with the hydroxyl value of 2mg KOH/g.

[ example 5 ]

The same procedure as in example 4 was repeated except that 700g of propylene oxide was used instead of the mixture of propylene oxide and ethylene oxide to obtain polyether polyol.

[ example 6 ]

The same procedure as in example 4 was repeated except that the mixture of propylene oxide and ethylene oxide was not added to obtain a polyether polyol.

[ example 7 ]

The same procedure as in example 4 was repeated except that 160g of a 2-functionality polyether polyol having a molecular weight of 400 was used instead of the 3-functionality polyether polyol having a molecular weight of 500 to obtain a polyether polyol.

[ example 8 ]

The same procedure as in example 4 was repeated, except that after obtaining a polyether having a hydroxyl value of 14mg KOH/g, 5g of NaH was added without capping with acetic anhydride, and after stirring at 45 ℃ for 1 hour, 30g of methyl iodide was added dropwise and reacted for 3 hours to obtain a polyether polyol.

[ COMPARATIVE EXAMPLE 1 ]

60g of glycerol and 4g of KOH are added into a 3L pressure kettle provided with a pressure and temperature meter, a stirring device and a raw material inlet. After nitrogen displacement, the temperature was raised to 100 ℃ and vacuum dehydration was carried out. Then the temperature was raised to 115 ℃ and 400g of ethylene oxide, then 1000g of propylene oxide and then 940g of butylene oxide were added. After the reaction was completed, 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, then 4.2g of aluminum silicate was added, vacuum dehydration was carried out, and the adsorbent was filtered to obtain 2385g of polyether polyol having no odor. According to the coacervation permeation chromatography using polystyrene as a standard, the number average molecular weight was 4210 and the molecular weight distribution was 1.15.

[ Experimental example ]

The cell opening agents prepared in examples 1-8 of the present invention and comparative example 1, the inlet cell opening agent Y-1900 and the inlet cell opening agent HKM-1 were used to prepare the slow rebound foam, the same formulation was used, the cell opening agents were added in an amount of 2 parts, and the results are shown in Table 1.

Table 1:

raw materials	Dosage (parts)
		GEP-560	30
GLR-2000	70
		H2O	1.5
Silicone oil	1
		Catalyst and process for preparing same	0.27
TDI	36.1
		Pore-forming agent	2

TABLE 2 aperturing Effect of polyether polyols prepared in the same Slow rebound formulation

As shown in Table 2, the cell opener and the inlet product Y-1900 of the invention are equivalent to the cell opener made in China in the aspect of shrinkage, and the preparation method is simpler than that of an alkaline catalyst. Meanwhile, compared with the comparative example 1 without adding cyclohexene oxide, the effect of the example is obviously improved.