CN109517353A - A kind of unsaturated polyester resin curing accelerator and its preparation method and application - Google Patents
A kind of unsaturated polyester resin curing accelerator and its preparation method and application Download PDFInfo
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- CN109517353A CN109517353A CN201811276904.1A CN201811276904A CN109517353A CN 109517353 A CN109517353 A CN 109517353A CN 201811276904 A CN201811276904 A CN 201811276904A CN 109517353 A CN109517353 A CN 109517353A
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- polyester resin
- unsaturated polyester
- curing accelerator
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- resin curing
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
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Abstract
The present invention provides a kind of unsaturated polyester resin curing accelerators and its preparation method and application.The unsaturated polyester resin curing accelerator includes having structure shown in logical formula (I) as follows:In the logical formula (I), R is hydrogen, halogen, alkyl, hydroxyalkyl, alkoxy, hydroxyl or alkylhalide group；R1For alkyl, hydroxyalkyl or alkaryl.Structure containing vinylacetate functional group and the specific combination of aniline function is innovatively used as the curing accelerator of unsaturated polyester resin by the present invention, the promotor is under the premise of guaranteeing rapid curing at room temperature, it can effectively improve the mechanical property of unsaturated polyester resin solidfied material, especially hardness Barcol, bending strength or impact strength.
Description
Technical field
The present invention relates to curing agent fields, more particularly, to a kind of unsaturated polyester resin curing accelerator and its system
Preparation Method and application.
Background technique
Unsaturated polyester resin refers to the linear alkyd resin in polymer chain containing unsaturated bond.These unsaturations are poly-
Ester resin is single by the way that styrene, vinyltoluene or diallyl phthalate etc. is added after polycondensation reaction
Body, polymerization inhibitor and promotor form pre-accelerated unsaturated polyester resin, carry out being crosslinked under the action of peroxide initiator solid
Change, forms the solid high molecular polymer with reticular structure.
In the presence of peroxide initiators, Tertiary amine accelerators are using a kind of relatively more extensive unsaturated polyester resin
Curing accelerator or accelerator.The market of requirement with to(for) room temperature curing is higher and higher, and alkyl amine is due to promoting low efficiency
Have been unable to meet the requirement of room temperature curing.Tertiary aromatic amine, as the Chinese invention patent of Publication No. CN101415762A discloses
N,N-Dimethylaniline, reactivity is higher, be usually used in the room temperature curing of unsaturated polyester resin, but its only with peroxidating
Object initiator for reaction, during the crosslinking curing that unsaturated-resin cannot be participated in, for final solid high molecular polymer power
Learning performance does not influence.
Existing promotor can not can improve on the basis of meeting room temperature curing in solid high molecular polymer power
Learn performance such as hardness Barcol, bending strength and impact strength etc..
Summary of the invention
The purpose of the present invention is to provide a kind of unsaturated polyester resin curing accelerator, unsaturated polyester resin solidifications
Promotor includes having the structure as shown in logical formula (I):
In the logical formula (I), R is hydrogen, halogen, alkyl, hydroxyalkyl, alkoxy, hydroxyl or alkylhalide group；R1For alkyl, hydroxyl
Alkyl or alkaryl.
Structure containing vinylacetate functional group and the specific combination of aniline function is innovatively used as not by the present invention
The curing accelerator of saturated polyester resin, under the premise of guaranteeing rapid curing at room temperature, which be can effectively improve
The mechanical property of unsaturated polyester resin solidfied material, especially hardness Barcol, bending strength or impact strength.
In a preferred embodiment of the invention, in the logical formula (I), R H, C1~C6Alkyl or C1~C6Hydroxyl
Alkyl；R1For C1~C6Alkyl or C2~C6Hydroxyalkyl.
In a preferred embodiment of the invention, in the logical formula (I), R is methyl, R1For methyl, ethyl or hydroxyl second
Base, further preferably methyl.Wherein, N- methyl para-totuidine has higher reactivity, while rate of rotation is high, without harsh
Reaction condition, and from a wealth of sources, cheap, the product room temperature solidification effect synthesized is preferable, and to mechanical property
Improve obvious.
Another object of the present invention is to provide a kind of preparation methods of unsaturated polyester resin curing accelerator, special
Sign is, comprising the following steps:
Aromatic amine is mixed with halogenated acetic acid vinyl acetate, under the action of acid binding agent, N- alkylated reaction obtain it is described not
Saturated polyester resin curing accelerator.
In a preferred embodiment of the invention, in order to further improve performance and promote reaction, aromatic amine is N's
Monosubstituted aromatic amine；Preferably methylphenylamine, N-ethylaniline, N- hydroxyethylaniline, N- methyl para-totuidine, N- ethyl pair
Toluidines, N- ethoxy para-totuidine it is one or more, further preferably N- methyl para-totuidine or N- ethoxy is to first
Aniline.
In a preferred embodiment of the invention, in order to preferably be reacted, the severity of reaction condition, institute are reduced
State halogenated acetic acid vinyl acetate be 1- vinyl chloroacetate, 1- bromo acetic acid vinyl acetate, one kind of 1- iodo vinylacetate or
It is a variety of, preferably 1- bromo acetic acid vinyl acetate.
In a preferred embodiment of the invention, acid binding agent is potassium carbonate, saleratus, potassium iodide, triethylamine, acetic acid
One of sodium, potassium acetate, cesium carbonate are a variety of, and in order to further be conducive to the separation of product after reaction, acid binding agent can
Think potassium carbonate.
In a preferred embodiment of the invention, higher aromatic amine conversion ratio, effectively reduces cost in order to obtain,
The aromatic amine, halogenated acetic acid vinyl acetate, the mass ratio of the material of acid binding agent are 1:(1~2): (1~2), preferably 1:(1~
1.2): (1~1.2).
In a preferred embodiment of the invention, the temperature of above-mentioned N- alkylated reaction is 30~80 DEG C, the time is 8~
16h。
In N- alkylated reaction of the invention, by aromatic amine, halogenated acetic acid vinyl acetate and tied up usually using organic solvent
Sour agent mixing.In a preferred embodiment of the invention, preparation method of the invention specifically comprises the following steps:
1) aromatic amine, acid binding agent are mixed with organic solvent according to the ratio, under the conditions of 30~80 DEG C, it is stirred to react 0.5~
2h；
2) halogenated acetic acid vinyl acetate is added into step 1) system according to the ratio, under the conditions of 30~80 DEG C, it is stirred to react 8~
16h, separating and filtering, remove organic solvent to get.
Wherein, in order to advanced optimize the reaction time, organic solvent can be DMF, THF or acetonitrile.Organic solvent adds
Enter 5~10 times that amount can be preferably aromatic amine mole.
Wherein, in the present invention, separating and filtering is usually that will isolate the organic layer in the mixed system after reacting, dry
Filtering.
Wherein it is possible to be prepared using the above method including having the unsaturated polyester (UP) tree as led to structure shown in formula (I)
Rouge curing accelerator:
If being prepared using the above method including having the unsaturated polyester resin solidification as led to structure shown in formula (I) to promote
Into agent, reaction mechanism can be with are as follows:
Wherein, X is halogen, preferably Cl, Br, I, further preferably Br.
A further object of the present invention is to provide the unsaturated polyester resin curing accelerators obtained by above-mentioned preparation method.
A further object of the present invention is to provide above-mentioned unsaturated polyester resin curing accelerator or above-mentioned preparation methods
Application of the obtained unsaturated polyester resin curing accelerator in unsaturated polyester resin solidifies.
The unsaturated polyester resin curing accelerator that the present invention obtains can be such that unsaturated polyester resin solidifies at room temperature,
Improve solid high molecular polymer mechanical property.The key technical indexes of unsaturated polyester resin curing accelerator of the invention
Are as follows: (1) gel time: under the conditions of 20 DEG C ± 2 DEG C ,≤20min；(2) peak temperature: >=105 DEG C ,≤140 DEG C；(3) when solidifying
Between: under the conditions of 20 DEG C ± 2 DEG C ,≤40min.Obtained resin solidification physical performance: (1) hardness Barcol: >=40；(2) bending strength:
≥105MPa；(3) impact strength: >=2.0KJ/m2。
Unsaturated polyester resin curing accelerator of the invention is particularly suitable for dicyclopentadiene type unsaturated polyester resin
Solidification can effectively improve its Pasteur's intensity, bending strength and impact strength, more preferably compared with other promotors
Ground can effectively make the gel time of promotor shorten (most short can be to 8.3min, 20 DEG C), peak temperature improves that (highest can
Up to 128 DEG C) and curing time reduce (most short can be to 15.5min, 20 DEG C).
Wherein, the curing system of dicyclopentadiene type unsaturated polyester resin is specifically included dicyclopentadiene type unsaturation
Polyester resin, 1,4-benzoquinone, initiator benzoyl peroxide and unsaturated polyester resin curing accelerator are uniformly mixed.
Compared with prior art, the invention has the benefit that
(1) unsaturated polyester resin curing accelerator prepared by the present invention, with traditional promotor the difference is that,
It has been grafted vinylacetate group on the N atom of aromatic amine, consolidating for unsaturated polyester resin and reactive diluent can be participated in
Change in cross-linking reaction, effectively improves the mechanical property of unsaturated polyester resin solidfied material, especially hardness Barcol, bending strength
Or impact strength；
(2) unsaturated polyester resin curing accelerator prepared by the present invention, in the case where working with peroxide one, Neng Gouman
The requirement of sufficient unsaturated polyester resin normal temperature cure；
(3) unsaturated polyester resin curing accelerator preparation method of the invention, reaction process is simple, reaction condition temperature
With, it is easy to accomplish.
Specific embodiment
With reference to embodiment, the embodiment of the present invention is furthur described in detail.Following embodiment is used for
Illustrate the present invention, but is used to limit the scope of the invention incessantly.
The commercially available acquisition of raw material components used in the present invention, agents useful for same of the embodiment of the present invention are that chemistry is pure.
Embodiment 1
A kind of unsaturated polyester resin curing accelerator is present embodiments provided, the preparation method is as follows:
1) N- methyl para-totuidine, 3mol acetonitrile, the 0.24mol triethylamine of 0.2mol are weighed, is put into reactor, control
Temperature is in 50 DEG C of ± 2 DEG C of stirring 1h；
2) it then weighs in the bromoacetic acid vinyl acetate investment reactor of 0.24mol, is heated to reflux, reaction is stirred under reflux
8h；
3) after reaction, reactant is added in separatory funnel, separates organic layer, dry (MgSO4) and filter, it depressurizes
Remove solvent.
Embodiment 2
A kind of unsaturated polyester resin curing accelerator is present embodiments provided, the preparation method is as follows:
1) N- ethoxy para-totuidine, 5mol acetonitrile, the 0.66mol triethylamine of 0.6mol are weighed, is put into reactor, control
Temperature processed is in 60 DEG C of ± 2 DEG C of stirring 1h；
2) it then weighs in the bromoacetic acid vinyl acetate investment reactor of 0.66mol, is heated to reflux, reaction is stirred under reflux
12h；
3) after reaction, reactant is added in separatory funnel, separates organic layer, dry (MgSO4) and filter, it depressurizes
Remove solvent.
Embodiment 3
A kind of unsaturated polyester resin curing accelerator is present embodiments provided, the preparation method is as follows:
1) N- ethyl-p-toluidiine, 4molTHF, 0.36mol potassium carbonate of 0.3mol are weighed, is put into reactor, control
Temperature is in 60 DEG C of ± 2 DEG C of stirring 0.5h；
2) it then weighs in the vinyl chloroacetate investment reactor of 0.36mol, is heated to reflux, reaction is stirred under reflux
12h；
3) after reaction, reactant is added in separatory funnel, separates organic layer, dry (MgSO4) and filter, it depressurizes
Remove solvent.
Embodiment 4
A kind of unsaturated polyester resin curing accelerator is present embodiments provided, the preparation method is as follows:
1) methylphenylamine, 5mol acetonitrile, 0.6mol diisopropylethylamine of 0.5mol are weighed, is put into reactor, control
Temperature processed is in 60 DEG C of ± 2 DEG C of stirring 0.5h；
2) it then weighs in the vinyl chloroacetate investment reactor of 0.6mol, is heated to reflux, reaction is stirred under reflux
12h；
3) after reaction, reactant is added in separatory funnel, separates organic layer, dry (MgSO4) and filter, it depressurizes
Remove solvent.
Embodiment 5
A kind of unsaturated polyester resin curing accelerator is present embodiments provided, the preparation method is as follows:
1) the N- hydroxyethylaniline, 10mol acetonitrile, 1.2mol potassium carbonate of 1mol are weighed, is put into reactor, temperature is controlled
In 50 DEG C of ± 2 DEG C of stirring 1h；
2) it then weighs in the iodoacetic acid vinyl acetate investment reactor of 1.2mol, is heated to reflux, reaction is stirred under reflux
10h；
3) after reaction, reactant is added in separatory funnel, separates organic layer, dry (MgSO4) and filter, it depressurizes
Remove solvent.
Embodiment 6
A kind of unsaturated polyester resin curing accelerator is present embodiments provided, the preparation method is as follows:
1) N-ethylaniline, 6mol acetonitrile, 0.6mol triethylamine of 0.5mol are weighed, is put into reactor, temperature is controlled
In 60 DEG C of ± 2 DEG C of stirring 1h；
2) it then weighs in the vinyl chloroacetate investment reactor of 0.6mol, is heated to reflux, reaction is stirred under reflux
8h；
3) after reaction, reactant is added in separatory funnel, separates organic layer, dry (MgSO4) and filter, it depressurizes
Remove solvent.
High activity unsaturated polyester resin curing accelerator prepared by Examples 1 to 6 is added to unsaturated polyester resin,
And it is detected.
Specific testing standard or method are as follows:
High activity unsaturated polyester resin curing accelerator 0.5g, dicyclopentadiene type obtained in Example 1~6 are not
Saturated polyester resin 100g and 1,4-benzoquinone 0.032g is uniformly mixed, and adds 1.5g initiator benzoyl peroxide, is uniformly mixed,
Gel time, peak temperature and curing time when according to 20 DEG C of GB/T 7193-2008 measurement；Corresponding solidfied material is taken to be placed in
96h in 20 DEG C of environment measures solidfied material by GB/T 2567-2008 by the hardness Barcol of GB/T 3854-2005 measurement solidfied material
Bending strength and impact strength, be as a result listed in table 1.
Taking market is often comparative example 1 with unsaturated polyester resin curing accelerator n,N-Dimethylaniline, by identical survey
Test-object is quasi- or method is tested.As a result it is listed in table 1.
Each embodiment of table 1 and comparative example data comparison
As known from Table 1, on gel and curing time, embodiment 1,2,3 has larger shortening compared with comparative example 1；It is real
Example 4,5,6 is applied compared with comparative example 1, though there is a degree of extension on the time, is still able to allow unsaturated polyester (UP) on the whole
Resin carries out rapid curing at normal temperature.In terms of unsaturated polyester resin solidfied material mechanical property, embodiment 1,2,3,4,5,6
Compared with comparative example 1, hardness Barcol, bending strength and impact strength all have a certain upgrade, and illustrate that unsaturation of the invention is poly-
Ester solidified resin promoter can improve the mechanical property of solidfied material.
Finally, method of the invention is only preferable embodiment, it is not intended to limit the scope of the present invention.It is all
Within the spirit and principles in the present invention, any modification, equivalent replacement, improvement and so on should be included in protection of the invention
Within the scope of.
Claims (10)
1. a kind of unsaturated polyester resin curing accelerator, which is characterized in that including having structure shown in logical formula (I) as follows:
In the logical formula (I), R is hydrogen, halogen, alkyl, hydroxyalkyl, alkoxy, hydroxyl or alkylhalide group；R1For alkyl, hydroxyalkyl or
Alkaryl.
2. unsaturated polyester resin curing accelerator according to claim 1, which is characterized in that in the logical formula (I), R
For H, C1~C6Alkyl or C1~C6Hydroxyalkyl；R1For C1~C6Alkyl or C2~C6Hydroxyalkyl.
3. unsaturated polyester resin curing accelerator according to claim 1, which is characterized in that in the logical formula (I), R
For methyl, R1For methyl, ethyl or ethoxy.
4. a kind of preparation method of unsaturated polyester resin curing accelerator, which comprises the following steps:
Aromatic amine is mixed with halogenated acetic acid vinyl acetate, under the action of acid binding agent, N- alkylated reaction obtains the unsaturation
Curable polyester resin promotor.
5. the preparation method according to claim 4, which is characterized in that
The aromatic amine is the monosubstituted aromatic amine of N；Preferably methylphenylamine, N-ethylaniline, N- hydroxyethylaniline, N- first
Base para-totuidine, N- ethyl-p-toluidiine, N- ethoxy para-totuidine it is one or more, further preferably N- methyl is to first
Aniline or N- ethoxy para-totuidine；
And/or the halogenated acetic acid vinyl acetate is 1- vinyl chloroacetate, 1- bromo acetic acid vinyl acetate, 1- iodo acetic acid second
One or more, the preferably 1- bromo acetic acid vinyl acetate of enester；
And/or the acid binding agent is potassium carbonate, in saleratus, potassium iodide, triethylamine, sodium acetate, potassium acetate, cesium carbonate
It is one or more, preferably potassium carbonate；
And/or use DMF, THF or acetonitrile for organic solvent in the N- alkylated reaction.
6. preparation method according to claim 4 or 5, which is characterized in that the aromatic amine, is tied up halogenated acetic acid vinyl acetate
The mass ratio of the material of sour agent is 1:(1~2): (1~2), preferably 1:(1~1.2): (1~1.2).
7. the preparation method according to any one of claim 4 to 6, which is characterized in that the temperature of the N- alkylated reaction
Degree is 30~80 DEG C, and the time is 8~16h.
8. preparation method according to any one of claims 4 to 7, which is characterized in that specifically comprise the following steps:
1) aromatic amine, acid binding agent are mixed according to the ratio with organic solvent, under the conditions of 30~80 DEG C, is stirred to react 0.5~2h；
2) halogenated acetic acid vinyl acetate is added into step 1) system according to the ratio and is stirred to react 8~16h under the conditions of 30~80 DEG C,
Separating and filtering, remove organic solvent to get.
9. preparation method according to any one of claims 4 to 8, which is characterized in that the unsaturated polyester resin is solid
Agent is unsaturated polyester resin curing accelerator as claimed any one in claims 1 to 3.
10. any in unsaturated polyester resin curing accelerator or claim 4 to 9 described in any one of claims 1 to 3
Application of the unsaturated polyester resin curing accelerator that preparation method described in obtains in unsaturated polyester resin solidifies.
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| CN201811276904.1A CN109517353B (en) | 2018-10-30 | 2018-10-30 | Unsaturated polyester resin curing accelerator and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5616564A (en) * | 1979-07-19 | 1981-02-17 | Hitachi Chem Co Ltd | Unsaturated polyester resin composition for coating metal |
| JPS5634717A (en) * | 1979-08-29 | 1981-04-07 | Hitachi Chem Co Ltd | Resin composition |
| CN104277186A (en) * | 2013-07-06 | 2015-01-14 | 常州华科聚合物股份有限公司 | Unsaturated resin composition, preparation method and use thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101757615B1 (en) * | 2009-01-30 | 2017-07-26 | 도다 고교 가부시끼가이샤 | Magnetic antenna, rf tag, and substrate having the rf tag mounted thereon |
-
2018
- 2018-10-30 CN CN201811276904.1A patent/CN109517353B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5616564A (en) * | 1979-07-19 | 1981-02-17 | Hitachi Chem Co Ltd | Unsaturated polyester resin composition for coating metal |
| JPS5634717A (en) * | 1979-08-29 | 1981-04-07 | Hitachi Chem Co Ltd | Resin composition |
| CN104277186A (en) * | 2013-07-06 | 2015-01-14 | 常州华科聚合物股份有限公司 | Unsaturated resin composition, preparation method and use thereof |
Non-Patent Citations (2)
| Title |
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| 任冬艳等: "《玻璃钢制品手糊及模压成型》", 30 June 2011, 武汉理工大学出版社 * |
| 王正熙等: "《高分子材料剖析方法与应用》", 31 January 2009, 上海科学技术出版社 * |
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