CN111732707B

CN111732707B - Macromonomer stabilizer and preparation method and application thereof

Info

Publication number: CN111732707B
Application number: CN202010646137.XA
Authority: CN
Inventors: 刘洋; 秦承群; 李付国; 刘斌; 殷玲; 陆国太; 石正阳; 姜明; 房士强; 黎源
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2020-07-07
Filing date: 2020-07-07
Publication date: 2022-07-12
Anticipated expiration: 2040-07-07
Also published as: CN111732707A

Abstract

The invention provides a macromolecular monomer stabilizer and a preparation method and application thereof, wherein polyether polyol is contacted with diisocyanate to react in the presence of a catalyst, and a compound with a structure shown in a formula I is added into the polyether polyol to continue to react to prepare the macromolecular monomer stabilizer; in the application process of the invention, in the presence of an initiator, a chain transfer agent and the macromolecular monomer stabilizer, polyether polyol is contacted with an ethylenically unsaturated monomer for polymerization reaction to prepare polymer polyol; the invention effectively enhances the stability of the polymer polyol by the dispersion action between unsaturated nitrogen heterocycle and ethylenic unsaturated monomer in the macromolecular monomer stabilizer, and the prepared polymer polyol has the advantages of low viscosity and uniform particle distribution

Description

Macromonomer stabilizer and preparation method and application thereof

Technical Field

The invention belongs to the technical field of stabilizers, and particularly relates to a preparation method and application of a macromonomer stabilizer for polymer polyol.

Background

Presently, known graft polyols include, for example, polyisocyanate polyaddition polyols, polyurea and/or polyhydrazodicarbonamide polyols and polymer polyols. The most widely used is polymer polyol (POP), mainly by synthesis of foams, elastomers, etc.

In order to improve the stability of polymer polyols, attempts have been made to modify polymer polyols, including specifically modifying the structure of polymer polyols, adjusting their formulation ratios, adjusting monomer ratios, and by modifying the macromer stabilizer. Among these, the methods by which the macromer stabilizer is introduced during the preparation are most effective, for example, CN105585652A discloses a method using macromer polymer polyols having specific reactive unsaturation; patent EP0786480B1 describes a process for preparing POP by a prepolymer process, in which a prepolymer is prepared from a macromer and an ethylenically unsaturated monomer under the action of an initiator, and is then polymerized with the ethylenically unsaturated monomer in a continuous polyether phase to prepare POP. At present, reactive macromer stabilizers are mainly described in the literature, but have limited dispersing properties.

In view of the foregoing, there is a need to develop a novel macromer stabilizer to improve the physical properties (e.g., dispersion stability, viscosity) of polymer polyols so that they can be easily controlled during subsequent use.

Disclosure of Invention

In view of the above, the present invention provides a method for preparing a macromonomer stabilizer, which is applied to a polymerization process of a polymer polyol, so that the polymer polyol has good dispersion stability and low viscosity.

In order to realize the purpose of the invention, the invention adopts the following technical scheme:

the first aspect of the invention provides a preparation method of a macromonomer stabilizer, which comprises the steps of contacting polyether polyol with diisocyanate to react in the presence of a catalyst, adding a compound with a structure shown in a formula I into the reaction product, and continuously reacting to obtain the macromonomer stabilizer;

the polyether polyol is added in an amount of 70-95% and preferably 80-90%, the diisocyanate is added in an amount of 2-20% and preferably 6-18%, and the compound with the structure shown in the formula I is 1-15% and preferably 2-12%, wherein the sum of the mass of the polyether polyol, the mass of the diisocyanate and the mass of the compound with the structure shown in the formula I is 100%;

in formula I, n is a positive integer of 1 or more, preferably 1 to 4, for example, 2, 3.

In the specific preparation process of the macromonomer stabilizer, the polyether polyol can be added in an amount of 75-85%, for example, 76%, 77%, 80%, 81%; the addition amount of the diisocyanate can be 10-17%, more preferably 10-14%, 14-16%, such as 11%, 15%; the addition amount of the compound with the structure shown in the formula I can be 5-10%, more preferably 6-8%, 8-9%, such as 7%, 8.5%.

The polyether polyol used in the invention can be obtained by ring opening of a small molecular initiator and an epoxy compound; as is well known to those skilled in the art, the small molecule starter may be selected from one or more of sucrose, sorbitol, pentaerythritol, trimethylolpropane, glycerol and ethylene glycol; the epoxy compound can be selected from one or more of ethylene oxide, propylene oxide, butylene oxide and oxacyclohexane, preferably a mixture of ethylene oxide and propylene oxide, and the specific preparation process belongs to the technical field and is not described in detail; meanwhile, the polyether polyol has an average nominal functionality of at least 2, preferably 3 to 6, such as 4, 5, and a number average molecular weight of 2000 to 8000g/mol, such as 3000g/mol or 5000 g/mol; the polyether polyols to be used in the present invention are also commercially available, for example, those sold under the trade designations F3135 and F3156 by Wanhua chemical Co., Ltd.

In the present invention, the diisocyanate is selected from one or more of toluene diisocyanate (abbreviated as "TDI"), diphenylmethane diisocyanate (abbreviated as "MDI") or isophorone diisocyanate (abbreviated as "IPDI"), and is preferably toluene diisocyanate.

In some embodiments of the present invention, the amount of the catalyst added is 0.1 to 2%, preferably 0.1 to 1%, such as 0.2%, 1.3%, 1.5%, based on 100% by mass of the sum of the polyether polyol, the diisocyanate, and the compound having the structure represented by formula i; the catalyst is selected from one or more of N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethanolamine, an organophosphorus catalyst, N '-diethylpiperazine, dimethylethanolamine or N, N' -dimethylpyridine; preferably triethanolamine or triethylamine.

In a specific embodiment of the invention, after the polyether polyol is contacted with diisocyanate, the reaction is carried out for 1-3 h at 10-100 ℃, then a compound with a structure shown as a formula I is added into the reaction for continuous reaction for 1-4 h, and then the reaction is cooled to room temperature to obtain the macromonomer stabilizer; preferably at 30-80 ℃.

In a second aspect, the present invention provides a macromonomer stabilizer obtained by the above preparation method.

The macromonomer stabilizer provided by the invention has an unsaturated nitrogen heterocyclic structure, the stability of molecules is effectively improved, and the stability is more excellent because the special structure of the stabilizer has dispersion attraction with unsaturated monomers.

In the third aspect of the invention, the application of the macromonomer stabilizer is provided, in the presence of an initiator, a chain transfer agent and the macromonomer stabilizer, polyether polyol is contacted with an ethylenically unsaturated monomer for polymerization reaction, and polymer polyol is prepared; wherein the macromolecular monomer stabilizer is prepared by the preparation method;

the addition amount of the macromolecular monomer stabilizer is 2-10%, preferably 4-8%, calculated by the sum of the mass of the initiator, the chain transfer agent, the macromolecular monomer stabilizer, the polyether polyol and the ethylenically unsaturated monomer being 100%.

In an embodiment of the application process of the present invention, the amount of the polyether polyol added is 30 to 80%, preferably 30 to 70%, more preferably 40 to 60%, for example, 45%, 50%, 55%, based on 100% of the sum of the mass of the initiator, the chain transfer agent, the macromer stabilizer, the polyether polyol and the ethylenically unsaturated monomer; the polyether polyol has an average nominal functionality of at least 2, preferably 3-6, and a number average molecular weight of 2000-8000; for example, 5000, 6000; polyether polyols available under the designations F3135, F3156 from Wanhua chemical group, Inc. may be used.

In a specific embodiment of the present invention, the amount of the ethylenically unsaturated monomer added is 10 to 60%, preferably 25 to 55%, more preferably 30 to 50%, for example, 34%, 40%, 45%, based on 100% by mass of the sum of the initiator, the chain transfer agent, the macromer stabilizer, the polyether polyol, and the ethylenically unsaturated monomer; the ethylenically unsaturated monomer may be selected from one or more of styrene, acrylonitrile, methacrylonitrile, vinylidene chloride, 1, 3-butadiene, isoprene or acrylates; in some preferred embodiments, the ethylenically unsaturated monomer may be styrene or a mixture of styrene and acrylonitrile, and the mass percentage of styrene in the mixture of styrene and acrylonitrile is 50 to 85%, more preferably 55 to 80%, such as 60%, 65%, and 70%.

In a specific embodiment of the invention, the addition amount of the initiator is 0.1-6%, preferably 1-5%, based on 100% of the sum of the mass of the initiator, the chain transfer agent, the macromonomer stabilizer, the polyether polyol and the ethylenically unsaturated monomer; the addition amount of the chain transfer agent is 0.5-5%;

the initiator is selected from peroxide and/or azo initiators, preferably selected from one or more of di (tert-butyl) -peroxide, tert-butyl peroxydiethylacetate, tert-butyl peroctoate, tert-butyl peroxy3, 5, 5-trimethylhexanoate, tert-butyl perbenzoate, tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, lauroyl peroxide, cumene hydroperoxide, tert-butyl peroxide, azobisisobutyronitrile or 2, 2' -azobis- (2-methylbutyronitrile); more preferably azobisisobutyronitrile;

the chain transfer agent is selected from water, isopropanol, 1-butanol, 2-butanol, mercaptan, ethanol or methanol, preferably mercaptan or isopropanol.

In some embodiments of the process for preparing polymer polyols, it is possible to carry out the process in a continuous manner, i.e.all the starting materials are mixed quantitatively with one another, introduced continuously into the reactor, reacted at a certain temperature and residence time and then transferred to a degassing process; alternatively, it can be carried out by a batch process, first placing the primers (chain transfer agent, stabilizer and part of polyether) in a reactor, then introducing the mixture of monomer, initiator and remaining raw materials into the reactor for a given time, and then carrying out the reaction at a certain temperature and residence time.

In the process of preparing the polymer polyol by the polymerization reaction, the temperature of the polymerization reaction is 50-150 ℃, and preferably 80-140 ℃; the pressure of the polymerization reaction is 0.1-1 MPa, preferably 0.3-0.6 MPa.

By adopting the technical scheme, the method has the following technical effects:

the invention takes the compound with the structure shown in the formula I as the raw material to prepare the novel macromolecular monomer stabilizer, and when the macromolecular monomer stabilizer is applied to the preparation process of polymer polyol, the stability of the polymer polyol is effectively enhanced through the dispersion force action between unsaturated nitrogen heterocycle and olefinic unsaturated monomer in the macromolecular monomer stabilizer, so that the obtained polymer polyol has the advantages of low viscosity and uniform particle distribution.

Detailed Description

In order to better understand the present invention, the following examples are provided to further illustrate the content of the present invention.

The following methods were used in each of the following examples to examine the properties of the polymer polyol:

(1) viscosity: measured by a Brookfield DV-II + Pro viscometer, and the used rotor is RV 6;

(2) stability: standing the polymer polyol at 40 ℃ for 1000h, and observing whether the polymer polyol is layered or not;

raw material source information in the following examples:

polyether polyol F3135: vanhua Chemicals group, Inc., functionality of 3, hydroxyl number of 35, number average molecular weight of 5000;

polyether polyol F3156: vanhua chemical group, Inc., functionality of 3, hydroxyl number of 56, number average molecular weight of 3000;

toluene Diisocyanate (TDI): vanhua chemical group, Inc.;

other chemical reagents used in the method adopt conventional reagents in the field, and the purity is higher than chemical purity.

Example 1

Adding 900g of polyether polyol F3135, 120g of Toluene Diisocyanate (TDI) and 1.5g of triethylamine into a 1.5L reactor provided with a stirrer, a heater, a thermocouple and a condensing device under the protection of nitrogen, uniformly mixing, reacting at 80 ℃ for 1 hour, adding 90g N- (hydroxymethyl) imidazole into a reaction system, continuously reacting for 2 hours, and cooling to room temperature to obtain the macromonomer stabilizer 1.

Example 2

Adding 850g of polyether polyol F3156, 180g of Toluene Diisocyanate (TDI) and 1.3g of triethylamine into a 1.5L reactor provided with a stirrer, a heater, a thermocouple and a condensing device under the protection of nitrogen, uniformly mixing, reacting at 80 ℃ for 1h, adding 80g N- (hydroxyethyl) imidazole into a reaction system, continuously reacting for 1h, and cooling to room temperature to obtain the macromonomer stabilizer 2.

Example 3

Adding 900g of polyether polyol F3135, 160g of Toluene Diisocyanate (TDI) and 1.3g of triethanolamine into a 1.5L reactor provided with a stirrer, a heater, a thermocouple and a condensing device under the protection of nitrogen, uniformly mixing, reacting at 100 ℃ for 3h, adding 110g N- (hydroxybutyl) imidazole into the reaction system, continuously reacting for 4h, and cooling to room temperature to obtain the macromonomer stabilizer 3.

The characterization data for the macromer stabilizer described above are as follows:¹⁵N-NMR:δ272.2,214,124.1.

in a reactor equipped with a stirrer, a heater, a thermocouple, and a condensing unit, 318g of polyether polyol F3135, 108g of macromer stabilizer 1, and 30g of isopropanol were added; then 250g of polyether polyol F3135, 4g of azobisisobutyronitrile and 371g of a mixture of styrene and acrylonitrile (the mass percentage of styrene in the mixture is 60%) are pumped into the reactor at a speed of 5 g/min; reacting at 100 + -2 deg.C under 0.5MPa for 3min to obtain polymer polyol 1.

According to the preparation method, 2-6 and 1-3 of polymer polyol are prepared, wherein the specific dosage of the raw materials is shown in Table 1;

TABLE 1

Note: in Table 1, the polyol is polymer polyol, for example, polyol 1 is polymer polyol 1.

The polymer polyol obtained above was subjected to viscosity and stability tests, and the test results are shown in table 2;

TABLE 2

Note: in the stability results in table 2, "√" indicates that no delamination was observed in the test, and "X" indicates that delamination was observed in the test.

Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.

Claims

1. A preparation method of a macromonomer stabilizer is characterized in that polyether polyol is contacted with diisocyanate to react in the presence of a catalyst, and then a compound with a structure shown in a formula I is added into the reaction to continue the reaction to prepare the macromonomer stabilizer;

the preparation method comprises the following steps of (1) adding 70-95% of polyether polyol, 2-20% of diisocyanate and 1-15% of a compound with the structure shown in the formula I, wherein the sum of the mass of the polyether polyol, the mass of the diisocyanate and the mass of the compound with the structure shown in the formula I is 100%;

in the formula I, n is a positive integer more than or equal to 1;

the polyether polyol has the number average molecular weight of 2000-8000 g/mol, and the diisocyanate is one or more selected from toluene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate.

2. The method according to claim 1, wherein the polyether polyol is added in an amount of 80 to 90%.

3. The method according to claim 1, wherein the diisocyanate is added in an amount of 6 to 18%.

4. The method according to claim 1, wherein the amount of the compound having the structure represented by formula I is 2-12%.

5. The method according to claim 1, wherein n is 1 to 4 in the formula I.

6. The method of claim 1, wherein the polyether polyol has an average nominal functionality of at least 2.

7. The method of claim 6, wherein the polyether polyol has an average nominal functionality of 3 to 6.

8. The method according to claim 6, wherein the diisocyanate is toluene diisocyanate.

9. The preparation method according to any one of claims 1 to 8, wherein the amount of the catalyst added is 0.1 to 2% based on 100% by mass of the sum of the polyether polyol, the diisocyanate and the compound having the structure represented by formula I;

the catalyst is selected from one or more of N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethanolamine, an organophosphorus catalyst, N '-diethylpiperazine, dimethylethanolamine or N, N' -dimethylpyridine.

10. The method according to claim 9, wherein the catalyst is added in an amount of 0.1 to 1%.

11. The method of claim 9, wherein the catalyst is selected from triethanolamine.

12. The method according to any one of claims 1 to 8 and 10 to 11, wherein the polyether polyol is reacted with the diisocyanate at 10 to 100 ℃ for 1 to 3 hours, and then the compound having the structure shown in the formula I is added.

13. The method of claim 12, wherein the polyether polyol is reacted with the diisocyanate at a temperature of 30 to 80 ℃.

14. A macromonomer stabilizer prepared by the method of any one of claims 1 to 13.

15. The application of the macromonomer stabilizer is characterized in that in the presence of an initiator, a chain transfer agent and the macromonomer stabilizer, polyether polyol is contacted with an ethylenically unsaturated monomer for polymerization reaction to prepare polymer polyol; wherein the macromonomer stabilizer is prepared by the preparation method of any one of claims 1 to 13, or the macromonomer stabilizer of claim 14;

the addition amount of the macromonomer stabilizer is 2-10% by taking the sum of the mass of the initiator, the chain transfer agent, the macromonomer stabilizer, the polyether polyol and the ethylenically unsaturated monomer as 100%.

16. Use according to claim 15, wherein the macromer stabiliser is added in an amount of 4-8%.

17. The use according to claim 15, wherein the polyether polyol is added in an amount of 30 to 80% based on 100% by mass of the sum of the initiator, the chain transfer agent, the macromer stabilizer, the polyether polyol and the ethylenically unsaturated monomer;

the polyether polyol has an average nominal functionality of at least 2 and a number average molecular weight of 2000-8000.

18. The use according to claim 17, wherein the polyether polyol is added in an amount of 30 to 70%.

19. Use according to claim 17, wherein the polyether polyol has an average nominal functionality of from 3 to 6.

20. The use according to any one of claims 15 to 19, wherein the ethylenically unsaturated monomer is added in an amount of 10 to 60% based on 100% by mass of the total of the initiator, the chain transfer agent, the macromer stabilizer, the polyether polyol and the ethylenically unsaturated monomer;

the ethylenically unsaturated monomer is selected from one or more of styrene, acrylonitrile, methacrylonitrile, vinylidene chloride, 1, 3-butadiene, isoprene or acrylates.

21. Use according to claim 20, wherein the ethylenically unsaturated monomer is added in an amount of 25 to 55%.

22. Use according to claim 20, wherein the ethylenically unsaturated monomer is selected from styrene or a mixture of styrene and acrylonitrile.

23. The use according to claim 22, wherein the mixture of styrene and acrylonitrile contains 50-85% by mass of styrene.

24. The use according to claim 23, wherein the mixture of styrene and acrylonitrile contains styrene in an amount of 55 to 80% by mass.

25. The use according to any one of claims 15 to 19 and 21 to 24, wherein the amount of the initiator added is 0.1 to 6% based on 100% by mass of the sum of the initiator, the chain transfer agent, the macromer stabilizer, the polyether polyol and the ethylenically unsaturated monomer;

the initiator is selected from peroxide and/or azo initiator;

the addition amount of the chain transfer agent is 0.5-5% by taking the sum of the mass of the initiator, the chain transfer agent, the macromonomer stabilizer, the polyether polyol and the ethylenically unsaturated monomer as 100%;

the chain transfer agent is selected from water, isopropanol, 1-butanol, 2-butanol, mercaptan, ethanol or methanol.

26. The use according to claim 25, wherein the initiator is added in an amount of 1 to 5%.

27. Use according to claim 25, wherein the initiator is selected from one or more of di (tert-butyl) -peroxide, tert-butyl peroxydiethylacetate, tert-butyl peroctoate, tert-butyl peroxy3, 5, 5-trimethylhexanoate, tert-butyl perbenzoate, tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, lauroyl peroxide, cumene hydroperoxide, azobisisobutyronitrile or 2, 2' -azobis- (2-methylbutyronitrile).

28. Use according to claim 27, wherein said initiator is selected from azobisisobutyronitrile.

29. Use according to claim 25, characterized in that the chain transfer agent is selected from mercaptans or isopropanol.

30. The use according to any one of claims 15 to 19, 21 to 24, 26 to 29, wherein the temperature of the polymerization reaction is 50 to 150 ℃; the pressure of the polymerization reaction is 0.1-1 MPa.

31. Use according to claim 30, wherein the polymerization temperature is from 80 to 140 ℃.

32. The use according to claim 30, wherein the polymerization pressure is 0.3 to 0.6 MPa.