CN114671996A - Polyurethane epoxy toughening agent and epoxy resin composition composed of same - Google Patents
Polyurethane epoxy toughening agent and epoxy resin composition composed of same Download PDFInfo
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- CN114671996A CN114671996A CN202210323389.8A CN202210323389A CN114671996A CN 114671996 A CN114671996 A CN 114671996A CN 202210323389 A CN202210323389 A CN 202210323389A CN 114671996 A CN114671996 A CN 114671996A
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Abstract
The invention belongs to the technical field of macromolecules, and particularly relates to a polyurethane epoxy toughening agent and an epoxy resin composition composed of the same. The molecular structure of the polyurethane epoxy toughening agent contains an epoxy group similar to that of the conventional epoxy resin and a chain segment structure similar to that of the conventional epoxy resin, and the polyurethane epoxy toughening agent has good compatibility with the epoxy resin; the toughening agent simultaneously contains an epoxy group and an acrylate group, and can generate chemical bonding with an epoxy resin matrix through an amine curing agent in the epoxy resin curing process, so that the high strength of the epoxy resin is ensured, and the high strength and high toughness of the epoxy resin are unified. The epoxy polyurethane epoxy toughening agent containing the epoxy group and the acrylate group can be used for preparing the high-strength high-toughness epoxy resin composition with the elongation at break of 30-100% by adjusting different effects, and has the advantages of wide formula application range and strong designability.
Description
Technical Field
The invention belongs to the technical field of macromolecules, and particularly relates to a polyurethane epoxy toughening agent and an epoxy resin composition composed of the same.
Background
The epoxy resin has excellent physical properties, chemical stability and the like, and is widely applied. But the epoxy resin has large brittleness and poor impact resistance. And limits the application field to a certain extent.
The polyurethane resin has good flexibility and high strength, can realize the unification of high strength and flexibility, and is one of materials commonly used for toughening epoxy resin. However, polyurethane resins have disadvantages for toughening epoxy resins. The isocyanate-terminated polyurethane resin has the defects of high toxicity, short storage period, poor storage stability and the like; the reaction between the isocyanate and the amine curing agent is very fast, and internal stress is easily formed in the material in the curing process, so that the defects of stress concentration and the like are easily generated in the material, and the risk of material failure is increased; the polyurethane resin without isocyanate group has few active groups and is difficult to form chemical bond connection with epoxy resin; easily cause macroscopic phase separation, can not realize the unification of high strength and flexibility, and is difficult to obtain ideal toughening effect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a polyurethane epoxy toughening agent containing epoxy groups and acrylate groups and a high-strength high-toughness epoxy resin composition consisting of the polyurethane epoxy toughening agent. The epoxy toughening agent contains active acrylate groups and epoxy groups, and can form chemical bond connection with an epoxy resin matrix in the curing process, so that high strength is ensured; meanwhile, the toughening agent contains epoxy groups and a chain segment structure similar to that of the conventional epoxy resin, has good compatibility with the epoxy resin, and does not generate macroscopic phase separation. The special molecular structure design of the epoxy toughening agent can toughen epoxy resin and simultaneously ensure the high strength of the epoxy resin, thereby realizing the unification of the high strength and the high toughness of the epoxy resin. The acrylic modified polyurethane epoxy toughening agent can be prepared with different effects, and is suitable for wide-range toughening and preparation with the elongation at break of 30-100%.
The polyurethane epoxy toughening agent contains epoxy groups and acrylate groups, and is obtained by the following method, and the concrete steps are as follows:
(1) mixing macrodiol, micromolecular diol, bisphenol A polyoxyethylene ether, epoxy resin and diisocyanate, and reacting at 70-95 ℃ for 2-3 hours to obtain a prepolymer;
(2) cooling to 60-85 ℃, adding an end-capping reagent into the prepolymer, and reacting for 2-4 h to obtain a polyurethane epoxy toughening agent containing an epoxy group and an acrylate group;
by mass ratio, macroglycol: small molecule dihydric alcohol: bisphenol a polyoxyethylene ether: epoxy resin: diisocyanate: the end-capping reagent is 30-80:0-5:5-20:5-20:40-60: 25-50.
The macrodiol is selected from polypropylene glycol or polytetrahydrofuran diol or polyester diol or polycaprolactone diol or polycarbonate diol or a mixture thereof; the molecular weight of the macrodiol is 500-3000.
The small molecule dihydric alcohol is selected from pentaerythritol diacrylate or ethylene glycol or butanediol or neopentyl glycol or a mixture thereof.
The diisocyanate is selected from isophorone diisocyanate or hexamethylene diisocyanate or 4,4 '-dicyclohexylmethane diisocyanate or toluene diisocyanate or diphenylmethane-4, 4' -diisocyanate or a mixture thereof.
The bisphenol A polyoxyethylene ether is selected from BPE-10 or BPE-20 or a mixture thereof.
The epoxy resin is an epoxy compound having an epoxy equivalent of 140-2000.
The epoxy resin is an epoxy compound having an epoxy equivalent of 140-: such as at least one of bisphenol A type epoxy resins (e.g., E-20, E-44, Dow DER331, south Asia NPEL-128S), bisphenol F type epoxy resins (e.g., Dow DER354, south Asia NPEF-170), novolac epoxy resins (e.g., Dow DER438, F-51), and epoxy diluents (e.g., Epodil 746, Epodil 750).
The end capping agent is selected from hydroxyethyl acrylate, hydroxypropyl acrylate, caprolactone acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate or their mixture.
The epoxy resin composition comprises the following components in parts by weight:
100 parts of epoxy resin;
30-100 parts of a polyurethane epoxy toughening agent;
25-50 parts of curing agent.
The epoxy resin is an epoxy compound having an epoxy equivalent of 140-2000.
The curing agent is selected from diethylenetriamine or isophorone diamine or polyether amine D230 or aminoethyl piperazine or a mixture thereof.
Compared with the prior art, the invention has the following beneficial effects:
the molecular structure of the polyurethane epoxy flexibilizer containing the epoxy group and the acrylate group contains the epoxy group and a chain segment structure similar to that of the conventional epoxy resin, has good compatibility with the epoxy resin, does not generate macroscopic phase separation, and effectively plays a toughening effect.
The epoxy group and the acrylate group in the molecular structure of the polyurethane epoxy flexibilizer containing the epoxy group and the acrylate group can generate chemical bonding with an epoxy resin matrix through an amine curing agent in the epoxy resin curing process, so that the high strength of the epoxy resin is ensured, and the high strength and high toughness of the epoxy resin are unified.
The epoxy polyurethane epoxy toughening agent containing the epoxy group and the acrylate group can be used for preparing the high-strength high-toughness epoxy resin composition with the elongation at break of 30-100% by adjusting different effects, and has the advantages of wide formula application range and strong designability.
Detailed Description
Example 1
The polyurethane epoxy toughening agent is characterized by comprising an epoxy group and an acrylate group, and is obtained by the following method, and the concrete steps are as follows:
a. mixing 30 parts of polycaprolactone diol (molecular weight 1000), 30 parts of polycaprolactone diol (molecular weight 3000), 5 parts of BPE-10, 10 parts of E-44 and 60 parts of 4,4' -dicyclohexylmethane diisocyanate, and reacting at 95 ℃ for 3 hours to obtain a prepolymer;
b. cooling to 85 ℃, adding 50 parts of dipentaerythritol pentaacrylate into the prepolymer, and reacting for 4 hours; obtaining a polyurethane epoxy flexibilizer containing epoxy groups and acrylate groups;
the epoxy resin composition comprises the following components in parts by weight:
DER 33190 parts of bisphenol A epoxy resin;
10 parts of bisphenol A epoxy resin NPEL-128S;
30 parts of the polyurethane epoxy toughening agent containing the epoxy group and the acrylate group;
23050 parts of polyether amine D;
the curing conditions were 25 ℃ for 7 days and the test results are summarized in table 1.
Example 2
The polyurethane epoxy toughening agent is characterized by comprising an epoxy group and an acrylate group, and is obtained by the following method, and the concrete steps are as follows:
a. mixing 20 parts of polytetrahydrofuran glycol (molecular weight is 1000), 10 parts of polypropylene glycol (molecular weight is 1000), 2 parts of ethylene glycol, 20 parts of BPE-20, 5 parts of E-20, 5 parts of DER331, 5 parts of NPEL-128S and 40 parts of isophorone diisocyanate, and reacting at 90 ℃ for 2 hours to obtain a prepolymer;
b. cooling to 75 ℃, adding 25 parts of hydroxyethyl acrylate into the prepolymer, and reacting for 2 hours to obtain a polyurethane epoxy toughening agent containing epoxy groups and acrylate groups;
the epoxy resin composition comprises the following components in parts by weight:
bisphenol F epoxy resin NPEF-170100 parts;
35 parts of the polyurethane epoxy flexibilizer containing the epoxy group and the acrylate group;
25 parts of diethylenetriamine;
the curing conditions were 25 ℃ for 7 days and the test results are summarized in Table 2.
Example 3
The polyurethane epoxy toughening agent is characterized by comprising an epoxy group and an acrylate group, and is obtained by the following method, and the concrete steps are as follows:
a. mixing 25 parts of polyester glycol (molecular weight of 3000), 25 parts of polypropylene glycol (molecular weight of 1000), 2 parts of neopentyl glycol, 10 parts of BPE-20, 2.5 parts of F-51, 2.5 parts of Epodil 746 and 45 parts of toluene diisocyanate, and reacting at 70 ℃ for 3 hours to obtain a prepolymer;
b. cooling to 60 ℃, adding 12.5 parts of pentaerythritol triacrylate and 15 parts of hydroxyethyl acrylate into the prepolymer, and reacting for 4 hours to obtain a polyurethane epoxy flexibilizer containing epoxy groups and acrylate groups;
the epoxy resin composition comprises the following components in parts by weight:
novolac epoxy resin F-5150 parts;
bisphenol A epoxy resin E-4445 parts;
epodil 7465 parts of epoxy diluent
100 parts of the polyurethane epoxy flexibilizer containing the epoxy group and the acrylate group;
23050 parts of polyether amine D;
the curing conditions were 25 ℃ for 7 days and the test results are summarized in Table 3.
Example 4
The polyurethane epoxy toughening agent is characterized by comprising an epoxy group and an acrylate group, and is obtained by the following method, and the concrete steps are as follows:
a. mixing 50 parts of polyester glycol (molecular weight 3000), 30 parts of polypropylene glycol (molecular weight 500), 2 parts of neopentyl glycol, 5 parts of BPE-10, 4.5 parts of E-20, 7.5 parts of DER354, 8 parts of NPEF-170 and 60 parts of diphenylmethane-4, 4' -diisocyanate, and reacting at 85 ℃ for 2 hours to obtain a prepolymer;
b. cooling to 75 ℃, adding 40 parts of acrylic caprolactone into the prepolymer, and reacting for 3 hours to obtain a polyurethane epoxy toughening agent containing an epoxy group and an acrylate group;
the epoxy resin composition comprises the following components in parts by weight:
bisphenol A epoxy resin E-2050 parts;
phenol epoxy DER4387.5 parts
DER 35435 parts of bisphenol F epoxy resin;
7507.5 parts of epoxy diluent Epodil
55 parts of the polyurethane epoxy toughening agent containing the epoxy group and the acrylate group;
35 parts of isophorone diamine;
the curing conditions were 25 ℃ for 7 days and the test results are summarized in Table 4.
Example 5
The polyurethane epoxy toughening agent is characterized by comprising an epoxy group and an acrylate group, and is obtained by the following method, and the concrete steps are as follows:
a. mixing 55 parts of polypropylene glycol (molecular weight 1000), 10 parts of polycarbonate diol (molecular weight 500), 1 part of butanediol, 4 parts of pentaerythritol diacrylate, 20 parts of BPE-10, 7.5 parts of DER438, 3 parts of Epodil 750 and 50 parts of hexamethylene diisocyanate, and reacting at 85 ℃ for 2 hours to obtain a prepolymer;
b. cooling to 75 ℃, adding 30 parts of hydroxypropyl acrylate into the prepolymer, and reacting for 2h to obtain a polyurethane epoxy toughening agent containing epoxy groups and acrylate groups;
the epoxy resin composition comprises the following components in parts by weight:
bisphenol A epoxy resin E-2070 parts;
bisphenol A epoxy resin E-4430 parts;
40 parts of the polyurethane epoxy toughening agent containing the epoxy group and the acrylate group;
25 parts of aminoethyl piperazine;
the curing conditions were 25 ℃ for 7 days and the test results are summarized in Table 5.
Claims (10)
1. The polyurethane epoxy toughening agent is characterized by comprising an epoxy group and an acrylate group, and is obtained by the following method, and the concrete steps are as follows:
(1) mixing macrodiol, micromolecular dihydric alcohol, bisphenol A polyoxyethylene ether, epoxy resin and diisocyanate, and reacting at 70-95 ℃ for 2-3 h to obtain a prepolymer;
(2) cooling to 60-85 ℃, adding an end-capping reagent into the prepolymer, and reacting for 2-4 h to obtain a polyurethane epoxy toughening agent containing an epoxy group and an acrylate group;
by mass ratio, macroglycol: small molecule dihydric alcohol: bisphenol a polyoxyethylene ether: epoxy resin: diisocyanate: the end capping agent is 30-80:0-5:5-20:5-20:40-60: 25-50.
2. The polyurethane epoxy toughening agent according to claim 1, wherein the macrodiol is selected from polypropylene glycol or polytetrahydrofuran diol or polyester diol or polycaprolactone diol or polycarbonate diol or a mixture thereof; the molecular weight of the macrodiol is 500-3000.
3. A polyurethane epoxy toughener as defined in claim 1 wherein the small molecule diol is selected from pentaerythritol diacrylate or ethylene glycol or butylene glycol or neopentyl glycol or mixtures thereof.
4. The polyurethane epoxy toughener of claim 1, wherein the diisocyanate is selected from isophorone diisocyanate or hexamethylene diisocyanate or 4,4 '-dicyclohexylmethane diisocyanate or toluene diisocyanate or diphenylmethane-4, 4' -diisocyanate or a mixture thereof.
5. The polyurethane epoxy toughener of claim 1, wherein the bisphenol a polyoxyethylene ether is selected from BPE-10 or BPE-20 or a mixture thereof.
6. The polyurethane epoxy toughening agent of claim 1, wherein the epoxy resin is an epoxy compound having an epoxy equivalent of 140-2000.
7. The polyurethane epoxy toughener as claimed in claim 1, wherein the end-capping agent is selected from hydroxyethyl acrylate, hydroxypropyl acrylate, caprolactone acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, or mixtures thereof.
8. The epoxy resin composition is characterized by comprising the following components in parts by weight:
100 parts of epoxy resin;
30-100 parts of a polyurethane epoxy toughening agent;
25-50 parts of curing agent.
9. The epoxy resin composition as claimed in claim 8, wherein the epoxy resin is an epoxy compound having an epoxy equivalent of 140-2000.
10. The epoxy resin composition of claim 8, wherein the curing agent is selected from diethylenetriamine or isophoronediamine or polyetheramine D230 or aminoethylpiperazine or mixtures thereof.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114605603A (en) * | 2022-03-30 | 2022-06-10 | 上海古原草科技有限公司 | Composite modified polyurethane epoxy toughening agent and epoxy resin composition composed of same |
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| CN114605603A (en) * | 2022-03-30 | 2022-06-10 | 上海古原草科技有限公司 | Composite modified polyurethane epoxy toughening agent and epoxy resin composition composed of same |
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