CN111777509A - Dihydric alcohol modified anhydride toughening agent - Google Patents
Dihydric alcohol modified anhydride toughening agent Download PDFInfo
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- CN111777509A CN111777509A CN202010524957.1A CN202010524957A CN111777509A CN 111777509 A CN111777509 A CN 111777509A CN 202010524957 A CN202010524957 A CN 202010524957A CN 111777509 A CN111777509 A CN 111777509A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/75—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a six-membered ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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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
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a dihydric alcohol modified anhydride toughening agent, which is characterized by being prepared by the following method: dehydrating the dihydric alcohol at 100 ℃ in vacuum, and introducing nitrogen after dehydration is finished; adding acid anhydride with an equal mole of acid anhydride functional group, reacting at the temperature of 100-150 ℃, and obtaining the dihydric alcohol modified acid anhydride toughening agent after the reaction is finished. The dihydric alcohol modified anhydride toughening agent can improve the elongation at break, so that the cured resin has higher toughness and the tensile strength meets the requirement. Has little influence on the glass transition temperature of a high-temperature curing system and has wide application prospect.
Description
Technical Field
The invention relates to the field of toughening agent preparation, in particular to a diol modified anhydride toughening agent.
Background
In the epoxy curing system, bisphenol A epoxy resin or bisphenol F epoxy resin is generally reacted with amine or anhydride curing agents, so that the application is wide. However, the brittleness of the epoxy resin directly influences the further use of the epoxy resin, and the problems of high brittleness and easy cracking are often encountered in many use occasions. Most formulations require toughening modifications to improve impact resistance and elongation at break of the article.
Generally, the strength and glass transition temperature of a cured product are sacrificed during toughening, so that a toughening agent which has small influence on the bulk strength and the glass transition temperature is necessary.
At present, most of toughening agents are epoxy resin modified products or rubber modified products, and the toughening agents need to be added into a main agent during application, so that the flexibility of the overall formula product is limited.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a diol modified anhydride toughening agent, which is added into a curing agent system during application, so that the flexibility of the system is greatly improved, the toughening effect is excellent, and the influence on the body strength and the glass transition temperature is small.
A diol modified anhydride toughening agent is prepared by the following method:
dehydrating the dihydric alcohol at 100 ℃ in vacuum, and introducing nitrogen after dehydration is finished;
adding acid anhydride with an equal mole of acid anhydride functional group, reacting at the temperature of 100-150 ℃, and obtaining the dihydric alcohol modified acid anhydride toughening agent after the reaction is finished.
In a preferred embodiment of the present invention, the diol comprises any one or more of ethylene glycol, 1, 2-butanediol, 1, 4-butanediol, 1, 6-hexanediol, 2-methyl-2, 4-pentanediol or 1, 2-propanediol.
Preferably 1, 4-butanediol, 1, 6-hexanediol or 2-methyl-2, 4-pentanediol.
In a preferred embodiment of the invention, the acid anhydride comprises any one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl nadic anhydride, maleic anhydride or phthalic anhydride.
Preferably any one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride or methyl nadic anhydride.
In a preferred embodiment of the present invention, the glycol-modified anhydride toughening agent is prepared by the following reaction method of formula 1:
in a preferred embodiment of the present invention, the glycol-modified anhydride toughening agent is prepared by the following reaction method of formula 2:
in a preferred embodiment of the present invention, the glycol-modified anhydride toughening agent is prepared by the following reaction method of formula 3:
in a preferred embodiment of the present invention, the glycol-modified anhydride toughening agent is prepared by the following reaction method of formula 4:
the invention has the beneficial effects that:
the dihydric alcohol modified anhydride toughening agent can improve the elongation at break, so that the cured resin has higher toughness and the tensile strength meets the requirement. Has little influence on the glass transition temperature of a high-temperature curing system and has wide application prospect.
Detailed Description
The design principle of the invention is as follows:
the product of the invention is modified anhydride, is added into a curing agent system when being applied, greatly improves the flexibility of the system, has excellent toughening effect and has small influence on the body strength and the glass transition temperature.
In the research process, the invention finds that the selection and control of the temperature have larger influence on the performance of the product, and the higher the temperature is, the more violent the polymerization reaction is.
Therefore, the toughening effect can meet the requirement by adjusting within the standard range. The products obtained by the same raw materials at different reaction temperatures are different, so the reaction temperature is set well in the synthesis process and controlled strictly.
When the reaction temperature is lower than 100 ℃, the ring opening of the anhydride is not easy, the reaction is weaker, and a brown yellow liquid is obtained. The toughening effect was not significant after addition to the curative system (as in comparative example 1). When the reaction temperature is higher than 150 ℃, the synthesis reaction is violent, the obtained product has higher crosslinking degree and can play a toughening effect, but the loss of the bulk strength is caused, and the loss of the glass transition temperature is larger (as a comparative example 2).
The invention is explained below with reference to specific embodiments:
example 1
A. Taking 80g of BDO into a flask, starting stirring, heating to 100 ℃, starting vacuum, heating to about 110 ℃, controlling the temperature to be 110 +/-5 ℃, and carrying out vacuum dehydration for 1 h;
B. and (3) closing the vacuum, adding 295g of MTHPA, greatly reducing the temperature, introducing nitrogen, raising the temperature to 110 ℃, controlling the temperature to be 110-120 ℃, and reacting for 1 h.
C. After the reaction is finished, discharging while the reaction is hot to obtain a brown yellow liquid which is solid at normal temperature.
In a curing system of an epoxy resin (A1) mainly containing 128 and a curing agent (B1) mainly containing MTHPA, 2 mass percent of BDO is added into B1 to modify the MTHPA to obtain B2. The data obtained by casting the sample were compared as follows: TABLE 1128/MTHPA System Add BDO modified MTHPA mechanical data sheet
TABLE 1128/MTHPA System Add BDO modified MTHPA mechanical data sheet
Note: a1, B1, A1 and B2 under the curing conditions of 100 ℃ and 3 h.
Example 2
A. Taking 100g of 1,6-HDO in a flask, starting stirring, heating to 100 ℃, starting vacuum, heating to about 110 ℃, controlling the temperature to be 110 +/-5 ℃, and carrying out vacuum dehydration for 1 h;
B. the vacuum is closed, the MTHPA 281g is added, the temperature is greatly reduced, nitrogen is introduced, the temperature is raised to 110 ℃, the temperature is controlled at 110 ℃ and 120 ℃, and the reaction is carried out for 1 h.
C. After the reaction is finished, discharging while the reaction is hot to obtain a brown yellow liquid which is solid at normal temperature.
In a curing system of an epoxy resin (A1) mainly containing 128 and a curing agent (B1) mainly containing MTHPA, 4 mass% of 1,6-HDO was added to B1 to modify MTHPA to obtain B3. The data obtained by casting the sample were compared as follows: TABLE 2128/MTHPA System Add HDO modified MTHPA mechanical data sheet
TABLE 2128/MTHPA System Add 1,6-HDO modified MTHPA mechanical data sheet
Note: a1, B1, A1 and B3 under the curing conditions of 100 ℃ and 3 h.
Example 3
A. Taking 80g of BDO into a flask, starting stirring, heating to 100 ℃, starting vacuum, heating to about 110 ℃, controlling the temperature to be 110 +/-5 ℃, and carrying out vacuum dehydration for 1 h;
B. and (3) closing the vacuum, adding 316g NMA, greatly reducing the temperature, introducing nitrogen, raising the temperature to 130 ℃, controlling the temperature to be 130-140 ℃, and reacting for 1 h.
C. After the reaction is finished, discharging while the reaction is hot to obtain a brown yellow liquid which is solid at normal temperature.
In a curing system of an epoxy resin (A2) mainly containing AG-80 and a curing agent (B4) mainly containing NMA, 2 mass percent of BDO (boron nitride oxide) is added into B4 to modify MTHPA, so that B5 is obtained. The data obtained by casting the sample were compared as follows:
TABLE 3 mechanics data sheet of adding BDO modified NMA to AG-80/NMA system
Note: a2: B4: A2: B5, the curing conditions were all 100 ℃ 1h +150 ℃ 1h +200 ℃ 1 h.
Example 4
The epoxy resin composition comprises the following raw materials in percentage by weight: 88% of bisphenol A epoxy resin (trade name E54) with the epoxy equivalent of 175-190 g/eq, 11% of 1, 4-butanediol diglycidyl ether and C12-C140.8 percent of alcohol glycidyl ether, 0.15 percent of propyl trimethoxy silane and 10100.05 percent of antioxidant.
The epoxy resin mixture comprises the following raw materials in percentage by weight: polyetheramine (D230) 67%, N-aminoethylpiperazine 30% and 2-phenylimidazole 3%.
The weight ratio of the component A to the component B is 100: 30.
The fiber-reinforced fabric has a modulus of 120000N/mm2The glass fiber of (2) accounts for 71% of the weight of the epoxy resin composition.
The viscosity of the epoxy resin mixture was determined to be 212mps using DIN 53015.
Example 5
A. Taking 100g of 1,6-HDO in a flask, starting stirring, heating to 100 ℃, starting vacuum, heating to about 110 ℃, controlling the temperature to be 110 +/-5 ℃, and carrying out vacuum dehydration for 1 h;
B. and (3) closing the vacuum, adding 302g of NMA, greatly reducing the temperature, introducing nitrogen, raising the temperature to 130 ℃, controlling the temperature to be 130-140 ℃, and reacting for 1 h.
C. After the reaction is finished, discharging while the reaction is hot to obtain a brown yellow liquid which is solid at normal temperature. The fiber-reinforced fabric has a modulus of 120000N/mm2The carbon fibers of (3) account for 71% by weight of the epoxy resin composition.
In a curing system of an epoxy resin (A2) mainly containing AG-80 and a curing agent (B4) mainly containing NMA, 4 mass percent of 1,6-HDO modified MTHPA is added into B4 to obtain B6. The data obtained by casting the sample were compared as follows:
TABLE 4 AG-80/NMA System addition 1,6-HDO modified NMA mechanical data sheet
Note: a2: B4: A2: B6, the curing conditions were all 100 ℃ 1h +150 ℃ 1h +200 ℃ 1 h.
Comparative example 1
A. Taking 100g of 1,6-HDO in a flask, starting stirring, heating to 100 ℃, starting vacuum, heating to about 110 ℃, controlling the temperature to be 110 +/-5 ℃, and carrying out vacuum dehydration for 1 h;
B. and (3) closing the vacuum, reducing the temperature to 100 ℃, adding 302g of NMA, greatly reducing the temperature, introducing nitrogen, heating to 90 ℃, controlling the temperature to be 85-95 ℃, and reacting for 1 h.
C. After the reaction is finished, discharging while the reaction is hot to obtain a brown yellow liquid which is solid at normal temperature. The fiber-reinforced fabric was carbon fiber with a modulus of 120000N/mm2, representing 71% by weight of the epoxy resin composition.
In a curing system of an epoxy resin (A2) mainly containing AG-80 and a curing agent (B4) mainly containing NMA, 4 mass percent of 1,6-HDO is added into B4 to modify MTHPA at a low temperature to obtain B7. The data obtained by casting the sample were compared as follows:
TABLE 5 mechanical data sheet of low temperature modified NMA with addition of HDO by AG-80/NMA system
Note: a2: B4: A2: B7, the curing conditions were all 100 ℃ 1h +150 ℃ 1h +200 ℃ 1 h.
Comparative example 2
A. Taking 100g of 1,6-HDO in a flask, starting stirring, heating to 100 ℃, starting vacuum, heating to about 110 ℃, controlling the temperature to be 110 +/-5 ℃, and carrying out vacuum dehydration for 1 h;
B. and (3) closing the vacuum, adding 302g of NMA, greatly reducing the temperature, introducing nitrogen, raising the temperature to 160 ℃, controlling the temperature to 160 ℃ and 170 ℃, and reacting for 1 h.
C. After the reaction is finished, discharging while the reaction is hot to obtain a brown yellow liquid which is solid at normal temperature. The fiber-reinforced fabric was carbon fiber with a modulus of 120000N/mm2, representing 71% by weight of the epoxy resin composition.
In a curing system of an epoxy resin (A2) mainly containing AG-80 and a curing agent (B4) mainly containing NMA, 4 mass percent of 1,6-HDO is added into B4 to modify MTHPA at a low temperature to obtain B8. The data obtained by casting the sample were compared as follows:
TABLE 6 mechanical data sheet of high temperature modified NMA by adding HDO into AG-80/NMA system
Note: a2: B4: A2: B8, the curing conditions were all 100 ℃ 1h +150 ℃ 1h +200 ℃ 1 h.
Claims (7)
1. The glycol modified anhydride toughening agent is characterized by being prepared by the following method:
dehydrating the dihydric alcohol at 100 ℃ in vacuum, and introducing nitrogen after dehydration is finished;
adding acid anhydride with an equal mole of acid anhydride functional group, reacting at the temperature of 100-150 ℃, and obtaining the dihydric alcohol modified acid anhydride toughening agent after the reaction is finished.
2. The glycol-modified anhydride toughening agent of claim 1, wherein the glycol comprises any one or more of ethylene glycol, 1, 2-butanediol, 1, 4-butanediol, 1, 6-hexanediol, 2-methyl-2, 4-pentanediol, or 1, 2-propanediol.
3. The glycol-modified anhydride toughening agent of claim 1, wherein the anhydride comprises any one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl nadic anhydride, maleic anhydride, or phthalic anhydride.
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Cited By (1)
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CN112708384A (en) * | 2021-02-24 | 2021-04-27 | 汕头市骏码凯撒有限公司 | Flexible toughening composition, toughening epoxy resin adhesive and preparation method thereof |
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CN1950424A (en) * | 2004-04-30 | 2007-04-18 | 东洋制罐株式会社 | Oxygen absorbing resin, oxygen absorbing resin composition and oxygen absorbing container |
CN102391482A (en) * | 2011-09-13 | 2012-03-28 | 江南大学 | Non-toxic environmentally friendly nadic anhydride polyester plasticizer and preparation method thereof |
CN103804670A (en) * | 2012-11-08 | 2014-05-21 | 上海凯众材料科技股份有限公司 | Polyester diol synthesis process |
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Patent Citations (3)
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CN1950424A (en) * | 2004-04-30 | 2007-04-18 | 东洋制罐株式会社 | Oxygen absorbing resin, oxygen absorbing resin composition and oxygen absorbing container |
CN102391482A (en) * | 2011-09-13 | 2012-03-28 | 江南大学 | Non-toxic environmentally friendly nadic anhydride polyester plasticizer and preparation method thereof |
CN103804670A (en) * | 2012-11-08 | 2014-05-21 | 上海凯众材料科技股份有限公司 | Polyester diol synthesis process |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN112708384A (en) * | 2021-02-24 | 2021-04-27 | 汕头市骏码凯撒有限公司 | Flexible toughening composition, toughening epoxy resin adhesive and preparation method thereof |
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Address after: 169 Leizhou Road, Fengxian District, Shanghai, 201419 Applicant after: Kangda new material (Group) Co.,Ltd. Address before: 169 Leizhou Road, Fengxian District, Shanghai, 201419 Applicant before: Shanghai Kangda Chemical New Material Group Co.,Ltd. |