CN111056976A - Urethane multi (methyl) acrylate and preparation method and application thereof - Google Patents
Urethane multi (methyl) acrylate and preparation method and application thereof Download PDFInfo
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- CN111056976A CN111056976A CN201911412587.6A CN201911412587A CN111056976A CN 111056976 A CN111056976 A CN 111056976A CN 201911412587 A CN201911412587 A CN 201911412587A CN 111056976 A CN111056976 A CN 111056976A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention discloses urethane multi (methyl) acrylate and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, performing ring-opening reaction on cyclic carbonate and organic amine to obtain carbamate polyol; s2, reacting the urethane polyol with (methyl) acrylate or (methyl) acrylic acid to obtain the urethane multi (methyl) acrylate. The preparation method provided by the invention does not need to use isocyanate, adopts relatively more environment-friendly raw materials and a chemical synthesis method, prepares the urethane polyol by catalyzing the reaction of cyclic carbonate and organic amine, and then prepares the radiation-curable urethane multi (methyl) acrylate by catalyzing ester exchange reaction or esterification reaction, and has lower cost. Moreover, the reaction efficiency of the ring-opening reaction can be obviously improved by using the lithium-containing catalyst, the reaction time is obviously shortened, and the method is favorable for industrial production.
Description
Technical Field
The invention relates to the technical field of preparation of carbamate, and particularly relates to a carbamate poly (methyl) acrylate and a preparation method and application thereof.
Background
When isocyanate is used for preparing radiation-curable urethane multi (meth) acrylate monomers, oligomers or high molecular polymers, the conventional preparation method adopts polyol, isocyanate and hydroxyethyl, propyl or butyl (meth) acrylate for preparation. For example, chinese patent application CN109071754A discloses a method for preparing urethane acrylates by using an isocyanate, a polyol and an end-capping agent containing an olefinic bond to obtain curable urethane acrylates.
The use of isocyanate leads to higher cost on one hand, and the isocyanate belongs to a highly toxic and dangerous chemical product on the other hand, and the production, storage and transportation all bring safety and environmental risks, especially at present, the environmental protection pressure is increasing day by day. The use of isocyanates such as TDI, MDI, IPDI or HDI as starting materials is subject to a number of transportation, storage and environmental constraints.
Therefore, there is a need to invent a more environmentally friendly preparation process, avoiding the use of isocyanates.
Disclosure of Invention
In order to overcome the defects of the prior art that isocyanate is needed, the cost is high and the environment is protected, the invention provides the preparation method of the urethane poly (meth) acrylate, the preparation method does not need to use isocyanate, adopts relatively more environment-friendly raw materials and a chemical synthesis method, and has low cost.
In order to solve the technical problems, the invention adopts the technical scheme that:
a process for preparing a urethane poly (meth) acrylate comprising the steps of:
s1, performing ring-opening reaction on cyclic carbonate and organic amine to obtain carbamate polyol; the organic amine is polyamine containing a plurality of primary amines or secondary amines, or alcohol amine containing one primary amine or secondary amine;
s2, reacting the urethane polyol with (methyl) acrylate or (methyl) acrylic acid to obtain the urethane multi (methyl) acrylate.
The preparation method provided by the invention does not need to use isocyanate, adopts relatively more environment-friendly raw materials and a chemical synthesis method, prepares the urethane polyol by reacting the cyclic carbonate with the organic amine, and then prepares the radiation-curable urethane multi (methyl) acrylate by catalyzing ester exchange reaction or esterification reaction, and has lower cost. The cyclic carbonate, such as ethylene carbonate or propylene carbonate, can be prepared by reacting ethylene oxide or propylene oxide with carbon dioxide, the ethylene carbonate or propylene carbonate has less environmental restriction compared with isocyanate, and is safer, carbon dioxide is used as a reaction raw material in the preparation process, the preparation process is a very green chemical reaction, and meanwhile, the product cyclic carbonate is also a green chemical product.
The prepared urethane multi (meth) acrylate is radiation curable, such as UV curable, and has good adhesion and also excellent cohesive strength.
And S1, carrying out ring opening reaction in an inert atmosphere. The inert atmosphere may be a nitrogen atmosphere.
Step S1. the ring opening reaction can be carried out by the existing reaction conditions. Specifically, in a nitrogen atmosphere, heating and stirring organic amine to 40-50 ℃, slowly dropwise adding cyclic carbonate, and reacting for 3-6 hours at 50 ℃ after dropwise adding. The amount of species of cyclic carbonates is equal to the total amount of species of primary and secondary amines in the organic amine.
However, the reaction efficiency of the reaction conditions is too low and the reaction time is too long, so that the industrial production needs are difficult to meet. The inventor finds that after the lithium-containing catalyst is added in the step S1, the reaction efficiency is greatly improved, the reaction time is obviously shortened, and the method is beneficial to industrial production.
Therefore, preferably, step s1. also adds a catalyst, which is a lithium-containing catalyst. Preferably, the catalyst is Li2O or LiBr. The addition amount of the catalyst can be 0.01-5.0%; for example, the amount added may be 0.01%, 0.1%, 0.2%, 3.5%, or 5.0%. The amount of catalyst added is calculated as the ratio of the mass of catalyst to the mass of all reactants.
Preferably, in the step S1, the reaction temperature is 40-110 ℃. For example, in step s1. the reaction temperature may be 40, 50, 80 or 110 ℃.
Preferably, the cyclic carbonate is a five-membered cyclic carbonate and/or a six-membered cyclic carbonate.
Preferably, the five-membered cyclic carbonate is one or more of ethylene carbonate, propylene carbonate or glycerol carbonate.
Preferably, the six-membered cyclic carbonate is one or more of 1, 3-propanediol cyclic carbonate, 2-methyl-1, 3-propanediol cyclic carbonate or neopentyl glycol cyclic carbonate.
Preferably, the organic amine is one or more of ethylenediamine, hexamethylenediamine, isophoronediamine, polyetheramine, monoethanolamine or diethanolamine.
The isophorone diamine is 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine.
Preferably, the polyether amine is a polyether diamine and/or a polyether triamine. The polyether diamine can be one or more of D230, D1000, D2000, D3000, D4000 or D5000. The polyether triamine can be T403 and/or T5000.
Preferably, the (meth) acrylate is one or more of methyl (meth) acrylate, ethyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate or n-butyl (meth) acrylate.
Preferably, step S2. reacting under the action of a transesterification catalyst and a polymerization inhibitor.
Preferably, the transesterification catalyst is lithium hydroxide.
Preferably, the polymerization inhibitor is a radical polymerization inhibitor. Preferably, the free radical polymerization inhibitor is hydroquinone monomethyl ether and/or 2-tert-butyl-4-methoxyphenol.
Preferably, in the step S2, the reaction temperature is 110-120 ℃, and the reaction time is 3-6 h.
The invention also protects the urethane multi (methyl) acrylate prepared by the preparation method.
The use of the urethane poly (meth) acrylates described above as crosslinkers for free-radical polymerization is also within the scope of the invention.
The invention also protects the use of the above urethane poly (meth) acrylates for the preparation of radiation curable compositions. The urethane poly (meth) acrylates can be used for preparing coatings, adhesives, leather finishing agents.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method provided by the invention does not need to use isocyanate, adopts relatively more environment-friendly raw materials and a chemical synthesis method, prepares the urethane polyol by reacting the cyclic carbonate with the organic amine, and then prepares the radiation-curable urethane multi (methyl) acrylate by catalyzing ester exchange reaction or esterification reaction, and has lower cost.
Moreover, the reaction efficiency of the ring-opening reaction can be obviously improved by using the lithium-containing catalyst, the reaction time is obviously shortened, and the method is favorable for industrial production.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The raw materials in the examples are all commercially available;
reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
A method for preparing a radiation curable urethane multi (meth) acrylate comprising the steps of:
s1, synthesis of urethane polyol: adding 122g (2.0mol) of monoethanolamine and 0.6g of catalyst lithium oxide into a 500mL four-neck flask, introducing nitrogen for protection, continuously stirring, heating to 40-50 ℃, slowly dropwise adding 176g (2.0mol) of ethylene carbonate, finishing adding half an hour, and continuously preserving heat at 50 ℃ for reaction until the monoethanolamine is completely consumed, wherein the reaction formula is as follows.
S2, synthesis of urethane multi (methyl) acrylate: adding 149 g (1mol) of the product obtained in the step S1, 0.1 g of N, N-dinaphthyl p-phenylenediamine and 3 ml of 2.5% lithium hydroxide methanol solution into a 500ml four-neck flask, installing a reflux condenser, adding methyl methacrylate (218g) (2.18mol), continuously stirring, adding a polymerization inhibitor hydroquinone monomethyl ether, heating to 115-120 ℃, continuously stirring and reacting for 4 hours, collecting and distilling 98.3% of theoretical methanol, and obtaining the following reaction formula.
Example 2
The method for preparing the radiation curable urethane multi (meth) acrylate of this example includes the steps of:
s1, synthesis of carbamic acid polyol: adding 120g (2.0mol) of ethylenediamine and 0.4g of catalyst lithium oxide into a 1000mL four-neck flask, introducing nitrogen for protection, continuously and mechanically stirring, heating to 40-50 ℃, slowly dropwise adding 352g (4.0mol) of ethylene carbonate, completing dropwise adding within 1 hour, carrying out exothermic reaction, keeping the temperature of reactants in a reaction bottle not more than 70 ℃, and continuing the reaction after the addition is completed until the ethylenediamine reaction is completed (titration), wherein the reaction formula is as follows.
S2, synthesis of urethane multi (methyl) acrylate: the procedure was as in step S2 of example 1, using the diol which was the product of step S1. of this example in 98.7% yield according to the following reaction scheme.
Example 3
The method for preparing the radiation curable urethane multi (meth) acrylate of this example includes the steps of:
s1, synthesis of urethane polyol: 232g of hexamethylenediamine flaky crystal (2.0mol) is added into a 1000mL four-neck flask, nitrogen is introduced for protection, the flask is heated to 50 ℃, continuous mechanical stirring is carried out, after all the hexamethylenediamine white crystal is melted into liquid, 0.58g of catalyst lithium oxide is added, 352g (4.0mol) of ethylene carbonate is slowly dripped, the dripping is completed within 1 hour, the temperature of reactants in the reaction flask is kept not more than 80 ℃ (exothermic reaction), the reaction is continued after the charging is completed until the hexamethylenediamine reaction is completed (titration), and the reaction formula is as follows.
S2, synthesis of urethane multi (methyl) acrylate: the procedure was as in step S2 of example 1, using the diol which was the product of step S1. of this example in 98.5% yield according to the following reaction scheme.
Example 4
The method for preparing the radiation curable urethane multi (meth) acrylate of this example includes the steps of:
s1, synthesis of urethane polyol: 170.3g (1.0mol) of 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine is added into a 500mL four-neck flask, nitrogen is introduced for protection, the mixture is heated to 45-50 ℃, continuously and mechanically stirred, 176g (2.0mol) of ethylene carbonate is dropwise added, the dropwise addition is completed within about 1 hour, the temperature of reactants in a reaction bottle is kept not more than 80 ℃ (exothermic reaction), after the addition is completed, the temperature is kept at 70 ℃, and the continuous stirring is carried out for 6 hours until the organic amine reaction is completed (titration), wherein the reaction formula is as follows.
S2, synthesis of urethane multi (methyl) acrylate: the procedure was as in step S2 of example 1, using the diol which was the product of step S1. of this example in 98.5% yield according to the following reaction scheme.
Example 5
The method for preparing the radiation curable urethane multi (meth) acrylate of this example includes the steps of:
s1, synthesis of urethane polyol: adding 176g (2mol) of ethylene carbonate into 1mol of polyetheramine D230 (molecular weight 232) or polyetheramine (D2000) with molecular weight 2000, heating to 45-50 ℃ under the protection of nitrogen until the organic amine is reacted, wherein the reaction formula is as follows.
S2, synthesis of urethane multi (methyl) acrylate: the procedure is as in step S2 of example 1, using the diol which is the product of step S1. of this example, in 98.1% yield.
Example 6
The method for preparing the radiation curable urethane multi (meth) acrylate of this example includes the steps of:
s1, synthesis of urethane polyol: 105 g (1mol) of diethanolamine and 204 g (2mol) of propylene carbonate were charged into a 500ml four-neck flask, heated to 80 ℃ and reacted with continuous stirring for various times, and then samples were taken respectively to titrate the remaining amine (unreacted amine content), and the results are shown in Table 1. In this example, the catalyst Li was added2O，Li2The mass ratio of O to the mass of all reactants was 0.2%. As control 1, no catalyst Li was added2O, other reaction conditions were the same as in this example.
TABLE 1
Note: a percent catalyst added based on total reactants.
b: after different times of reaction, the ratio of the titrated amine content to the amine content at reaction time 0.
As can be seen from Table 1, in the absence of catalyst, propylene carbonate and secondary amine were substantially unreactive, and after the addition of 0.2% lithium oxide, the reaction rate increased dramatically, and 85% of the reaction was completed in 20 minutes, while in control 1, 20 minutes, which was no catalyst, the reaction was only 2%.
S2, synthesis of urethane multi (methyl) acrylate: the method may refer to step S2 of example 1.
Example 7
The method for preparing the radiation curable urethane multi (meth) acrylate of this example includes the steps of:
s1, synthesis of urethane polyol: 204 g (2mol) of propylene carbonate and 232g of polyetheramine D230(1mol) were put into a 1000ml four-necked flask, heated to 110 ℃ and reacted with stirring continuously for various periods of time, and then the remaining amine (unreacted amine content) was sampled and titrated, and the results are shown in Table 2. In this example, a catalyst LiBr was added, and the mass ratio of LiBr to the total reactant mass was 3.5%. As control 2, no LiBr catalyst was added, and the other reaction conditions were the same as in this example.
TABLE 2
Note: a percent catalyst added based on total reactants.
b: after different times of reaction, the ratio of the titrated amine content to the amine content at reaction time 0.
Table 2 clearly shows that without catalyst, the reaction at 110 ℃ for 120 minutes converted only 20%, with a conversion of up to 62% with the same temperature and reaction time as the addition of 3.5% lithium bromide. From the results, it can be found that the lithium-containing catalyst greatly accelerates the reaction speed, shortens the reaction time, and has very important significance for industrial production.
S2, synthesis of urethane multi (methyl) acrylate: the method may refer to step S2 of example 1.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A method for preparing urethane multi (meth) acrylate, characterized by comprising the steps of:
s1, performing ring-opening reaction on cyclic carbonate and organic amine to obtain carbamate polyol; the organic amine is polyamine containing a plurality of primary amines or secondary amines, or alcohol amine containing one primary amine or secondary amine;
s2, reacting the urethane polyol with (methyl) acrylate or (methyl) acrylic acid to obtain the urethane multi (methyl) acrylate.
2. The preparation method according to claim 1, wherein a catalyst is further added in step s1, and the catalyst is a lithium-containing catalyst.
3. The method according to claim 2, wherein the catalyst is Li2O or LiBr.
4. The method according to claim 2 or 3, wherein the reaction temperature in step S1 is 40-110 ℃.
5. The production method according to claim 1, wherein the cyclic carbonate is a five-membered cyclic carbonate or a six-membered cyclic carbonate; the five-membered cyclic carbonate is one or more of ethylene carbonate, propylene carbonate or glycerol carbonate; the six-membered cyclic carbonate is one or more of 1, 3-propanediol cyclic carbonate, 2-methyl-1, 3-propanediol cyclic carbonate or neopentyl glycol cyclic carbonate.
6. The preparation method according to claim 1, wherein the organic amine is one or more of ethylenediamine, hexamethylenediamine, isophoronediamine, polyetheramine, monoethanolamine, and diethanolamine.
7. The preparation method of claim 1, wherein the (meth) acrylate is one or more of methyl (meth) acrylate, ethyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate or n-butyl (meth) acrylate.
8. Urethane poly (meth) acrylate obtained by the production method according to any one of claims 1 to 7.
9. Use of the urethane poly (meth) acrylates according to claim 8 as crosslinkers for free radical polymerization.
10. Use of the urethane poly (meth) acrylates according to claim 8 for the preparation of radiation curable compositions.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111978880A (en) * | 2020-08-07 | 2020-11-24 | 湖南尚鑫新材料科技有限公司 | High-compression-resistance antifogging film and preparation method thereof |
| CN112029399A (en) * | 2020-08-17 | 2020-12-04 | 湖南尚鑫新材料科技有限公司 | Antifogging coating and preparation method thereof |
| CN112457816A (en) * | 2020-12-14 | 2021-03-09 | 山东华诚高科胶粘剂有限公司 | Adhesive for yellowing-resistant adhesive stone permeable pavement and application thereof |
| WO2021231212A1 (en) * | 2020-05-11 | 2021-11-18 | Momentive Performance Materials Inc. | Additives for producing polyurethanes |
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| CN112029399A (en) * | 2020-08-17 | 2020-12-04 | 湖南尚鑫新材料科技有限公司 | Antifogging coating and preparation method thereof |
| CN112457816A (en) * | 2020-12-14 | 2021-03-09 | 山东华诚高科胶粘剂有限公司 | Adhesive for yellowing-resistant adhesive stone permeable pavement and application thereof |
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Application publication date: 20200424 |
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| RJ01 | Rejection of invention patent application after publication |