CN112062937B - Carbamate-based epoxy compounds, methods of making, and uses thereof - Google Patents
Carbamate-based epoxy compounds, methods of making, and uses thereof Download PDFInfo
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- CN112062937B CN112062937B CN202010852100.2A CN202010852100A CN112062937B CN 112062937 B CN112062937 B CN 112062937B CN 202010852100 A CN202010852100 A CN 202010852100A CN 112062937 B CN112062937 B CN 112062937B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
Abstract
The invention discloses an epoxy compound based on carbamate, a preparation method and application thereof, and belongs to the field of synthesis of the epoxy compound based on carbamate. The method comprises the following steps: (1) preparing an oligomer containing hydroxyl and epoxy groups; (2) And preparing an oligomer which is terminated by an epoxy group and contains a carbamate structure. The epoxy compound prepared by the invention can be cured by using the traditional ammonia curing agent and the traditional acid anhydride curing agent. When the ammonia curing agent is adopted to prepare the casting body, the resin gel time and the operability time are obviously longer than those of polyurethane resin with the same structure, and the mechanical property of the casting body has the advantages of epoxy resin and polyurethane resin, and has high rigidity and good toughness.
Description
Technical Field
The invention belongs to the field of synthesis of epoxy compounds of carbamate, and particularly relates to an epoxy compound based on carbamate, and a preparation method and application thereof.
Background
The polyurethane resin has the advantages of high curing speed, high production efficiency, good product flexibility and the like, and is increasingly applied to the field of preparation of fiber reinforced composite materials under different processes. Because the activity of the polyurethane resin is too high, the traditional direct glue preparation of epoxy, unsaturated, vinyl, phenolic resin and the like cannot be adopted to be placed in an open glue groove of a production line when in use, and independent and closed two-component glue supply system equipment must be added, so that the production mode that the resin is mixed at present and used, the glue is supplied immediately, and the amount of the mixed resin is used is realized. In the prior art, for example, patents CN2014108544600, CN2017800245049, CN2015202971151, CN2018200936617, CN2019104552070, CN2016102900507, CN2010800545234 and CN201280006798X, CN2015107959358 are all pultrusion process production methods adopting the above technical means. For the production processes of hand pasting, winding and the like, such as adding a two-component glue supply system, on one hand, the increase of equipment causes the increase of production cost, and on the other hand, the addition of a new system increases the complexity of the production process. The two-component glue supply system cannot be added for the vacuum infusion process at all.
The epoxy resin system solidified by adopting the amino and the epoxy group has long enough gel time, has the advantage of long operability time when producing hand paste products, large winding products and large vacuum infusion products, and in addition, the cured epoxy resin has high rigidity and brittleness, is superior to polyurethane resin in the properties of stretching, bending and the like, and is inferior to the polyurethane resin in the properties of impact resistance, bending resistance and the like.
Therefore, there is a need to develop a new resin system which can simultaneously achieve the long gel time and high rigidity of the epoxy resin and the impact resistance and high flexibility of the polyurethane resin.
Disclosure of Invention
The purpose of the invention is as follows: there are provided a urethane-based epoxy compound, a preparation method and an application thereof to solve the problems involved in the background art as described above.
The technical scheme is as follows: the invention provides a preparation method of an epoxy compound based on carbamate, which comprises the following steps:
step one, preparing an oligomer containing hydroxyl and epoxy groups:
heating a monomer containing two or more epoxy groups to 80-120 ℃, vacuumizing to remove water for 0.5-2 hours, adding a small molecular monocarboxyl compound and a certain amount of catalyst according to the molar ratio of the epoxy group monomer to carboxyl of 1 (0.8-1.2) within the range of 80-140 ℃, and reacting for 0.5-4 hours to obtain an oligomer containing both hydroxyl and epoxy groups;
step two, preparing an oligomer which is terminated by an epoxy group and contains a carbamate structure:
adding isocyanate compound according to the molar ratio of the isocyanate group to the hydroxyl group of 1 (0.8-1.2) at normal temperature, and continuously reacting for 6-10 hours to obtain the epoxy-terminated carbamate mixture.
As a preferred embodiment, the epoxy monomer has the general formula:
wherein the value of n is 2-4.
As a preferable scheme, when the value of n of the epoxy monomer general formula is 2, the monomer can be selected from one or a mixture of more of ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether.
As a preferable scheme, when the value of n of the epoxy monomer formula is 3, the monomer can be one or a mixture of glycerol triglycidyl ether, trimethylolpropane triglycidyl ether and polyether polyol triglycidyl ether with the functionality of 3.
As a preferable scheme, when the value of n of the general formula of the epoxy monomer is 4, the epoxy monomer can be selected from one or more of pentaerythritol tetraglycidyl ether or polyether polyol tetraglycidyl ether with a functional group of 4.
Preferably, the small molecule monocarboxyl compound is one of acetic acid, propionic acid, butyric acid and valeric acid.
As a preferable scheme, the catalyst is one of p-toluenesulfonic acid, triphenylphosphine and triethylamine.
As a preferable mode, the amount of the catalyst is 0.1 to 1% by weight based on the total weight of the reaction system.
As a preferable scheme, the isocyanate is one or more of polymeric diphenylmethane diisocyanate (polymeric MDI), 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, toluene Diisocyanate (TDI), isophorone diisocyanate, hexamethylene Diisocyanate (HDI) and hydrogenated diphenylmethane diisocyanate (HMDI).
The invention also provides an epoxy compound, oligomer or mixture of the carbamate obtained by the preparation method or the synthetic route, namely, the carboxyl is adopted to open the ring of partial epoxy, and then the hydroxyl generated by the ring opening is utilized to react with the isocyanate group, so that the residual epoxy group is connected to the original isocyanate group through the establishment of the carbamate group.
The invention also provides an application of the carbamate epoxy compound, oligomer or mixture in the production of hand paste products, large winding products and large vacuum infusion products, and a using method of the carbamate epoxy compound, oligomer or mixture comprises the following steps:
step one, preparing an epoxy compound, an oligomer or a mixture of the carbamate;
and step two, curing the epoxy compound, oligomer or mixture of the carbamate by using primary amino-terminated polyether with the molecular weight of 800-1200g/mol and the functionality of 2 to produce hand paste products, large winding products and large vacuum infusion products.
Has the beneficial effects that: the invention relates to an epoxy compound based on carbamate, a preparation method and application thereof, and compared with the prior art, the method has the following advantages: (1) Compared with the traditional epoxy resin, the epoxy compound has the advantages that the impact resistance and the flexibility of a casting body of the epoxy compound are obviously improved when the polyether amine is used for curing, and the epoxy compound is equivalent to the well-known polyurethane resin with good flexibility; (2) Compared with the traditional polyurethane resin, the epoxy compound has obviously prolonged operable time when being cured by adopting the polyether amine, is equivalent to the acknowledged epoxy resin, unsaturated resin and the like with long operating time, and has obvious advantages for producing large-scale composite material products; and (3) the cost is not obviously increased. The invention is modified on the basis of polyurethane resin raw materials, and finally cured by adopting an epoxy group curing mode. The polyurethane resin in China has huge raw material productivity and cheap raw materials, and the price of the modified carbamate epoxy resin is even lower than that of the traditional epoxy resin.
Detailed Description
The invention will now be further described with reference to the following examples, which are intended to be illustrative of the invention and are not to be construed as limiting the invention. The examples, where specific techniques and reaction conditions are not indicated, can be carried out according to the techniques or conditions or product specifications described in the literature in the field. Reagents, instruments or equipment of any manufacturer not indicated are commercially available.
Example 1
Heating 2020g of butanediol diglycidyl ether to 120 ℃, vacuumizing to remove water for 1 hour, adding 600g of acetic acid and 13.1g of triphenylphosphine catalyst according to the molar ratio of the ethylene glycol diglycidyl ether to carboxyl of 1:1 at 80 ℃, reacting for 4 hours to obtain a compound simultaneously containing hydroxyl and epoxy, adding 1250g of 2, 4-diphenylmethane diisocyanate and 4,4-diphenylmethane diisocyanate mixture (any ratio) at normal temperature according to the molar ratio of isocyanate to hydroxyl of 1:1, and continuously reacting for 6 hours to obtain the epoxy-terminated carbamate mixture.
Example 2
Heating 2572g of a mixture of butanediol diglycidyl ether (1212 g) and bisphenol A diglycidyl ether (1360 g) to 120 ℃, vacuumizing to remove water for 1 hour, adding 740g of acetic acid and 6.63g of triethylamine catalyst at 100 ℃ according to the molar ratio of the 2 glycidyl ethers to the carboxyl group of 1:1, reacting for 3 hours to obtain a compound simultaneously containing a hydroxyl group and an epoxy group, adding 1102g of an isocyanate mixture of polymeric MDI (667 g) and toluene diisocyanate (435 g) according to the molar ratio of the isocyanate group to the hydroxyl group of 1:1, and continuously reacting for 8 hours to obtain an epoxy group-terminated urethane mixture.
Example 3
Heating 3020g of trimethylolpropane triglycidyl ether to 120 ℃, vacuumizing to remove water for 1 hour, adding 880g of butyric acid and 39g of p-toluenesulfonic acid catalyst according to the molar ratio of glycidyl ether to carboxyl 1:1 at 140 ℃, reacting for 0.5 hour to obtain a compound simultaneously containing hydroxyl and epoxy, adding 1334g of polymeric MDI according to the molar ratio of isocyanate to hydroxyl of 1:1 at normal temperature, and continuing to react for 10 hours to obtain an epoxy-terminated carbamate mixture.
Example 4
2852g of a mixture of trimethylolpropane triglycidyl ether (1812 g) and glycerol triglycidyl ether (1040 g) is heated to 120 ℃, vacuumized to remove water for 1 hour, 1020g of valeric acid and 23.2g of triphenylphosphine catalyst are added at 120 ℃ according to the molar ratio of the glycidyl ether to carboxyl of 1:1 to react for 1.5 hours to obtain a compound simultaneously containing hydroxyl and epoxy groups, 1110g of isophorone diisocyanate is added at normal temperature according to the molar ratio of the isocyanate group to the hydroxyl group of 1:1, and the reaction is continued for 7 hours to obtain an epoxy-terminated carbamate mixture.
Example 5
3600g of pentaerythritol glycidyl ether is heated to 120 ℃, vacuum pumping is carried out to remove water for 1 hour, 1020g of valeric acid and 13.86g of triphenylphosphine catalyst are added at 90 ℃ according to the molar ratio of the glycidyl ether to carboxyl of 1:1 to react for 3.5 hours to obtain a compound simultaneously containing hydroxyl and epoxy, a mixture of 420g of hexamethylene diisocyanate and 645g of hydrogenated diphenylmethane diisocyanate is added at normal temperature according to the molar ratio of isocyanate to hydroxyl of 1:1, and the reaction is continued for 9 hours to obtain an epoxy-terminated carbamate mixture.
Example 6
Heating 1800g of pentaerythritol glycidyl ether and 2000g of polyether polyol (PN 560, kunshan chemical engineering) with functionality of 4 and molecular weight of 400g/mol to 120 ℃, vacuumizing for dewatering for 1 hour, adding 600g of valeric acid and 30.8g of triethylamine catalyst according to the molar ratio of glycidyl ether to carboxyl of 1:1 at 110 ℃, reacting for 1 hour to obtain a compound simultaneously containing hydroxyl and epoxy groups, adding a mixture of 252g of hexamethylene diisocyanate and 903g of hydrogenated diphenylmethane diisocyanate according to the molar ratio of isocyanate groups to hydroxyl of 1:1, and continuously reacting for 9 hours to obtain an epoxy-terminated carbamate mixture.
Example 7
Heating 2020g of butanediol diglycidyl ether to 80 ℃, vacuumizing to remove water for 2 hours, adding 600g of acetic acid and 13.1g of triphenylphosphine catalyst according to the molar ratio of the ethylene glycol diglycidyl ether to carboxyl being 1.
Example 8
Heating 2020g of butanediol diglycidyl ether to 120 ℃, vacuumizing to remove water for 0.5 hour, adding 600g of acetic acid and 13.1g of triphenylphosphine catalyst according to the molar ratio of the ethylene glycol diglycidyl ether to carboxyl being 1.
The epoxy oligomers prepared in examples 1 to 6 were cured with a primary amino-terminated polyether having a molecular weight of 1000g/mol and a functionality of 2 and tested for gel time (min), tensile strength (MPa) and elongation at break (%) at 25 ℃.
Preparation of comparative examples 1 to 6:
curing was carried out using the isocyanates (compositions) used in examples 1 to 6, respectively, and a secondary hydroxypolyether having a molecular weight of 1000g/mol and a functionality of 2, and the gel time (min), tensile strength (MPa) and elongation at break (%) at 25 ℃ were measured.
As can be seen from the test data in the table above, the resin system prepared by the invention has obviously prolonged gel time compared with the polyurethane resin system, obviously improved tensile strength compared with the polyurethane resin, and the elongation at break is equal to that of the polyurethane system. Basically realizes the functions of long gel time of an epoxy system, high product rigidity and good toughness of a polyurethane system.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
Claims (9)
1. Use of a mixture of epoxy-terminated urethanes to produce hand-lay-up products, large wound products and large vacuum infusion products, in a method comprising the steps of:
step one, preparing a mixture of epoxy-terminated carbamate; the preparation method of the mixture of the epoxy-terminated carbamate comprises the following steps: 1. preparing an oligomer containing hydroxyl and epoxy groups: heating a monomer containing binary or more epoxy groups to 80-120 ℃, vacuumizing to remove water for 0.5-2 hours, adding a small-molecule monocarboxyl compound and a certain amount of catalyst according to the molar ratio of the epoxy group monomer to carboxyl of 1 (0.8-1.2) within the range of 80-140 ℃, and reacting for 0.5-4 hours to obtain an oligomer simultaneously containing hydroxyl and epoxy groups; 2. preparation of epoxy group-terminated oligomer containing carbamate structure: adding isocyanate compound at normal temperature according to the molar ratio of isocyanate group to hydroxyl group of 1 (0.8-1.2), and continuously reacting for 6-10 hours to obtain the mixture of the carbamate with the blocked epoxy group;
and step two, curing the mixture of the epoxy-terminated carbamate by primary amino-terminated polyether with the molecular weight of 800-1200g/mol and the functionality of 2 to produce hand paste products, large winding products and large vacuum infusion products.
2. The use according to claim 1, wherein the monomer having two or more epoxy groups has the formula:
wherein the value of n is 2-4.
3. The use of claim 2, wherein when the monomer containing two or more epoxy groups has a general formula of 2, the monomer is selected from one or more of ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.
4. The use according to claim 2, wherein the monomer containing two or more epoxy groups has a general formula wherein n is 3, and is selected from one or more of glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and polyether polyol triglycidyl ether having a functionality of 3.
5. The use according to claim 2, wherein when the monomer containing two or more epoxy groups has a general formula of n of 4, the monomer is selected from one or more of pentaerythritol tetraglycidyl ether or polyether polyol tetraglycidyl ether having a functional group of 4.
6. The use of claim 1, wherein the small molecule monocarboxyl compound is one of acetic acid, propionic acid, butyric acid and valeric acid.
7. The use of claim 1, wherein the catalyst is one of p-toluenesulfonic acid, triphenylphosphine and triethylamine.
8. The use according to claim 1, wherein the amount of the catalyst is 0.1 to 1% by weight based on the total weight of the reaction system.
9. The use of claim 1, wherein the isocyanate is one or more of polymeric diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.
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| CN113637388A (en) * | 2021-08-20 | 2021-11-12 | 国网福建省电力有限公司电力科学研究院 | Isocyanate-based epoxy resin antirust primer |
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| CN109721708A (en) * | 2018-12-19 | 2019-05-07 | 上海乘鹰新材料有限公司 | A kind of epoxy acrylate oligomer and the preparation method and application thereof |
| CN111171240A (en) * | 2020-01-19 | 2020-05-19 | 南京聚发新材料有限公司 | Resin for mould pressing process, preparation method and application thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03115318A (en) * | 1989-09-27 | 1991-05-16 | Dainippon Toryo Co Ltd | Epoxy resin for coating material |
| US5334654A (en) * | 1993-05-03 | 1994-08-02 | Air Products And Chemicals, Inc. | Flexibilized polyepoxide resins |
| JP2004107610A (en) * | 2002-09-18 | 2004-04-08 | Kenji Ema | Polyurethane resin containing epoxy group |
| CN106752852A (en) * | 2017-03-21 | 2017-05-31 | 新疆科能防水防护技术股份有限公司 | A kind of epoxy resin modification agent and preparation method thereof |
| CN109721708A (en) * | 2018-12-19 | 2019-05-07 | 上海乘鹰新材料有限公司 | A kind of epoxy acrylate oligomer and the preparation method and application thereof |
| CN111171240A (en) * | 2020-01-19 | 2020-05-19 | 南京聚发新材料有限公司 | Resin for mould pressing process, preparation method and application thereof |
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