CN107573456A - A kind of high adhesion force without benzene Hydroxylated acrylic resin and preparation method thereof - Google Patents
A kind of high adhesion force without benzene Hydroxylated acrylic resin and preparation method thereof Download PDFInfo
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- CN107573456A CN107573456A CN201710729870.6A CN201710729870A CN107573456A CN 107573456 A CN107573456 A CN 107573456A CN 201710729870 A CN201710729870 A CN 201710729870A CN 107573456 A CN107573456 A CN 107573456A
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- benzene
- acrylic resin
- high adhesion
- adhesion force
- hydroxylated acrylic
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Abstract
A kind of high adhesion force of the present invention without benzene Hydroxylated acrylic resin and preparation method thereof, according to mass percent, including 40~50Wt% of non-toluene solvent, 5~15Wt% of isobornyl methacrylate, 5~10Wt% of cyclohexyl methacrylate, 10~20Wt% of n-BMA, 5~15Wt% of lauryl methacrylate, 0~10Wt% of hydroxy propyl methacrylate, 0~10Wt% of hydroxyethyl methacrylate, 0~1Wt% of methacrylic acid, 0.1~1Wt% of mixing addition catalyst.There can be preferable adhesive force on the special substrate that the conventional resins such as stainless steel are difficult to adhere to；Its feature, which also resides in, can be not required to high-temperature baking and reach the purpose of solidification, save the energy；Also reside in and be free of harmful free phenyl ring.Coating made of the present invention be not in storage, construction layering, it is anti-slightly and gel, be coated directly onto on difficult attachment ground, have good adhesive force after drying.
Description
Technical field
The invention belongs to technical field of macromolecules, specifically, be related to a kind of high adhesion force without benzene hydroxy acrylic acid tree
Fat and preparation method thereof.
Background technology
With the development in pluralism of hardware industry, glass industry and ceramic industry, various hardware, glass, ceramics are due to it
Each there is the advantages of a variety of, and the use extensively sent out in daily life.Simultaneously in order to improve their surfaces dicoration with
Protectiveness, application spray painting often is carried out to their surfaces.But so far, the metal works for some more difficult attachments,
Glass and ceramics, such as：Aluminium, aluminium alloy, kirsite, stainless steel, magnesium alloy, plated item, safety glass, on surface
Ceramics of glaze etc., it is more difficult attachment to paint in these surface of bottom material.
Traditional paint is often made with high temperature amino-stoving varnish, by pyroreaction with adding adhesion promoter in paint
Or coupling agent is undoubtedly to reach the excellent effect of adhesive force, but for not possessing the producer of high-temperature reaction equipment
One problem, it is severe plus pyroreaction power consumption, cost is aggravated, and also it is now more and more stricter to environmental requirement, based on a variety of
Reason, so working out some has fine adhesive force in difficult attachment material and can be applied and applied with the environment-friendly resin of low-temp reaction
After in material, reach the purpose that spraying can directly adhere on various metalworks, glass, ceramics, this is that this area needs to solve at present
Technical problem certainly.
In order to solve this technical problem, professional to acrylic resin generally by being modified, such as by drawing
Enter epoxy resin, polyester resin is modified, by introduce chelating agent, adhesion promoter be modified the methods of.It is but above-mentioned
Among method of modifying, although the advantages of having introduced modifying agent, the shortcomings that also having introduced modifying agent simultaneously, some ask all be present
Topic.Such as polyester modification is introduced, it can be short of in terms of dryness with hardness, water resistance, sometimes for reaching and polyester components
Compatible purpose and sacrifice weatherability.Introducing adhesion promoter would generally then cause manufactured coating to go out in storage, construction
Now layering, anti-thick even gel, influence to use.
The content of the invention
Instant invention overcomes in the prior art the shortcomings that, there is provided a kind of high adhesion force without benzene Hydroxylated acrylic resin and
Its preparation method, its be a kind of environmental protection can low-temp reaction the resin good in substrate adhesions such as stainless steels, while remain third
All advantages of olefin(e) acid resin.
In order to solve the above-mentioned technical problem, the present invention is achieved by the following technical solutions：
A kind of high adhesion force without benzene Hydroxylated acrylic resin, according to mass percent, including non-toluene solvent 40~
50Wt%, 5~15Wt% of isobornyl methacrylate, 5~10Wt% of cyclohexyl methacrylate, n-BMA
10~20Wt%, 5~15Wt% of lauryl methacrylate, 0~10Wt% of hydroxy propyl methacrylate, hydroxyethyl methacrylate second
0~10Wt% of ester, 0~1Wt% of methacrylic acid, 0.1~1Wt% of mixing addition catalyst.
Further, the non-toluene solvent refers to the solvent without free benzene.
Further, non-toluene solvent butyl acetate, butanone or the propylene glycol methyl ether acetate.
Further, the mixing addition catalyst refers to peroxide or azo compound without phenyl ring.
Further, the mixing addition catalyst refers to peroxide -2-ethyl hexanoic acid tert-butyl, peroxidating di tert butyl carbonate
Or azodiisobutyronitrile.
A kind of preparation method without benzene Hydroxylated acrylic resin of high adhesion force, comprises the following steps：
1st, the air led in nitrogen displacement reactor, by the rebasing addition reactor of part non-toluene solvent；
2nd, it is warming up to certain temperature；
3rd, monomer mixture and part non-toluene solvent is added dropwise within a period of time and mixes the mixing of addition catalyst
Thing, and a period of time is incubated, monomer mixture refers to isobornyl methacrylate, cyclohexyl methacrylate, methyl
N-butyl acrylate, lauryl methacrylate, hydroxy propyl methacrylate, hydroxyethyl methacrylate and methacrylic acid
Mixture；
4th, remaining mixing addition catalyst and part non-toluene solvent mixture are added, and is incubated a period of time；
5th, cool, add remaining non-toluene solvent, filtering and discharging.
Further, in step 2, temperature is 100 DEG C~105 DEG C.
Further, in step 3, the monomer mixture time for adding is 1~20 hour.
Further, in step 3, the soaking time is 1 to 5 hour.
Further, in step 4, the soaking time is 1 to 10 hours.
Compared with prior art, the beneficial effects of the invention are as follows：
A kind of high adhesion force of the present invention without benzene Hydroxylated acrylic resin and preparation method thereof, can be in stainless steel
There is preferable adhesive force on the special substrate for being difficult to adhere to etc. conventional resins；Its feature, which also resides in, can be not required to high-temperature baking and reach
To the purpose of solidification, the energy is saved；Also reside in and be free of harmful free phenyl ring.Coating made of the present invention storage,
Be not in construction layering, it is anti-slightly and gel, be coated directly onto on difficult attachment ground, have good adhesive force after drying.
Embodiment
The preferred embodiments of the present invention are illustrated below, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1：
A kind of high adhesion force without benzene Hydroxylated acrylic resin, according to mass percent, including non-toluene solvent 45Wt%, first
Base isobornyl acrylate 15Wt%, cyclohexyl methacrylate 5Wt%, n-BMA 11Wt%, metering system
Sour lauryl 15Wt%, hydroxyethyl methacrylate 8.5Wt%, mixing addition catalyst 0.5Wt%.
Its preparation method：The 28Wt% non-toluene solvents of oeverall quality are put into reactor, are warming up to 125 DEG C to 130 DEG C,
The mixed of the mixture of whole monomers and 0.4Wt% mixed catalyst and 8Wt% non-toluene solvent is uniformly added dropwise in 3 hours
Compound, in 125 DEG C to 130 DEG C insulation reactions 2 hours after dripping off, add the nothing of remaining 0.1Wt% mixed catalysts and 1Wt%
Benzene solvent, then insulation reaction 3 hours, cooling, add remaining 8Wt% non-toluene solvents, stir discharging, gets product.
Embodiment 2：
A kind of high adhesion force without benzene Hydroxylated acrylic resin, according to mass percent, including non-toluene solvent 50Wt%, first
Base isobornyl acrylate 5Wt%, cyclohexyl methacrylate 10Wt%, n-BMA 18Wt%, metering system
Sour lauryl 8Wt%, hydroxy propyl methacrylate 8.5Wt%, methacrylic acid 0.3Wt%, mix addition catalyst
0.2Wt%.
Its preparation method：The 20Wt% non-toluene solvents of oeverall quality are put into reactor, are warming up to 125 DEG C to 130 DEG C,
The mixing of the mixed catalyst of whole monomer mixtures and 0.15Wt% and 9Wt% non-toluene solvent is uniformly added dropwise in 3 hours
Thing, in 125 DEG C to 130 DEG C insulation reactions 2 hours after dripping off, remaining 0.05Wt% mixed catalysts and 1Wt% are added without benzene
The mixture of solvent, then insulation reaction 3 hours, cooling, add remaining 20Wt% non-toluene solvents, stir discharging, produces
Finished product.
The resin of the present invention and the resin of same use type on the market are done into performance comparison, detailed comparisons are listed below
Table：
| Index contrasts | With moral ACR6688 | Embodiment 1 | Embodiment 2 | Diana LR7602 |
| Gu contain (%) | 60.68 | 55.6 | 50.8 | 49.81 |
| Acid value (mgKOH/g) | 3.46 | 0.5 | 2.5 | 1.87 |
| Viscosity (CPS/30 DEG C) | 3800 | 2500 | 2000 | 3200 |
| Hydroxyl value | 66 (2.0%) | 66 (2.0%) | 66 (2.0%) | 66 (2.0%) |
Paint film property contrast is as follows：
Note：Adhesive force rank by being well to difference：0 grade of 1 grade of ＞, 2 grades of ＞, 3 grades of ＞, 4 grades of ＞ ＞, 5 grades of ＞ are without adhesive force.
Contrasted from upper table, adhesive force of the embodiments of the invention on various metal substrates is all relatively good.Than one
It is outstanding with the same kind of products at abroad contrasted is done.Wherein with moral ACR6688 on the various metals in addition to stainless steel ground
Adhesive force is best, and only on stainless steel without adhesive force, the present invention is that the present invention is not because change to this one kind effectively supplement
Property, the shortcomings that without introducing other modifying agent.
Finally it should be noted that：The preferred embodiments of the present invention are these are only, are not intended to limit the invention, although
The present invention is described in detail with reference to embodiment, for those skilled in the art, it still can be to foregoing
Technical scheme described in each embodiment is modified, or to which part technical characteristic carry out equivalent substitution, but it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements made etc., the protection of the present invention should be included in
Within the scope of.
Claims (10)
1. a kind of high adhesion force without benzene Hydroxylated acrylic resin, it is characterised in that according to mass percent, including non-toluene solvent
40~50Wt%, 5~15Wt% of isobornyl methacrylate, 5~10Wt% of cyclohexyl methacrylate, methacrylic acid is just
10~20Wt% of butyl ester, 5~15Wt% of lauryl methacrylate, 0~10Wt% of hydroxy propyl methacrylate, methacrylic acid
0~10Wt% of hydroxyl ethyl ester, 0~1Wt% of methacrylic acid, 0.1~1Wt% of mixing addition catalyst.
2. according to claim 1 a kind of high adhesion force without benzene Hydroxylated acrylic resin, it is characterised in that the no benzene is molten
Agent refers to the solvent without free benzene.
3. according to claim 2 a kind of high adhesion force without benzene Hydroxylated acrylic resin, it is characterised in that the no benzene is molten
Agent butyl acetate, butanone or propylene glycol methyl ether acetate.
4. according to claim 1 a kind of high adhesion force without benzene Hydroxylated acrylic resin, it is characterised in that it is described mixing plus
Peroxide or azo compound without phenyl ring are referred into catalyst.
5. according to claim 4 a kind of high adhesion force without benzene Hydroxylated acrylic resin, it is characterised in that it is described mixing plus
Peroxide -2-ethyl hexanoic acid tert-butyl, peroxidating di tert butyl carbonate or azodiisobutyronitrile are referred into catalyst.
A kind of 6. preparation method without benzene Hydroxylated acrylic resin of high adhesion force according to claim 1, it is characterised in that
Comprise the following steps：
1st, the air led in nitrogen displacement reactor, by the rebasing addition reactor of part non-toluene solvent；
2nd, it is warming up to certain temperature；
3rd, monomer mixture and part non-toluene solvent is added dropwise within a period of time and mixes the mixture of addition catalyst, and
And insulation a period of time, monomer mixture refer to isobornyl methacrylate, cyclohexyl methacrylate, methacrylic acid
The mixing of N-butyl, lauryl methacrylate, hydroxy propyl methacrylate, hydroxyethyl methacrylate and methacrylic acid
Thing；
4th, remaining mixing addition catalyst and part non-toluene solvent mixture are added, and is incubated a period of time；
5th, cool, add remaining non-toluene solvent, filtering and discharging.
A kind of 7. preparation method without benzene Hydroxylated acrylic resin of high adhesion force according to claim 6, it is characterised in that
In step 2, temperature is 100 DEG C~105 DEG C.
A kind of 8. preparation method without benzene Hydroxylated acrylic resin of high adhesion force according to claim 6, it is characterised in that
In step 3, the monomer mixture time for adding is 1~20 hour.
A kind of 9. preparation method without benzene Hydroxylated acrylic resin of high adhesion force according to claim 6, it is characterised in that
In step 3, the soaking time is 1 to 5 hour.
10. a kind of preparation method without benzene Hydroxylated acrylic resin of high adhesion force, its feature exist according to claim 6
In in step 4, the soaking time is 1 to 10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710729870.6A CN107573456B (en) | 2017-08-23 | 2017-08-23 | High-adhesion benzene-free hydroxyl acrylic resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710729870.6A CN107573456B (en) | 2017-08-23 | 2017-08-23 | High-adhesion benzene-free hydroxyl acrylic resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107573456A true CN107573456A (en) | 2018-01-12 |
| CN107573456B CN107573456B (en) | 2020-06-02 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710729870.6A Active CN107573456B (en) | 2017-08-23 | 2017-08-23 | High-adhesion benzene-free hydroxyl acrylic resin and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627377A (en) * | 2018-12-12 | 2019-04-16 | 英德市雅家涂料有限公司 | A kind of ultrafast dry type automobile varnish hydroxy propylene acid resin and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101659726A (en) * | 2009-09-25 | 2010-03-03 | 北京红狮漆业有限公司 | Benzene-free acrylic resin and preparation method thereof |
| CN103130944A (en) * | 2013-02-21 | 2013-06-05 | 西安交通大学 | Preparation method of high-reaction-activity hydroxyl acrylic resin |
| CN103992428A (en) * | 2013-02-19 | 2014-08-20 | 上海飞凯光电材料股份有限公司 | Acrylate resin, preparation method and application thereof |
| CN105884966A (en) * | 2016-06-12 | 2016-08-24 | 上海未泉新材料科技有限公司 | High-adhesion acrylic resin |
-
2017
- 2017-08-23 CN CN201710729870.6A patent/CN107573456B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101659726A (en) * | 2009-09-25 | 2010-03-03 | 北京红狮漆业有限公司 | Benzene-free acrylic resin and preparation method thereof |
| CN103992428A (en) * | 2013-02-19 | 2014-08-20 | 上海飞凯光电材料股份有限公司 | Acrylate resin, preparation method and application thereof |
| CN103130944A (en) * | 2013-02-21 | 2013-06-05 | 西安交通大学 | Preparation method of high-reaction-activity hydroxyl acrylic resin |
| CN105884966A (en) * | 2016-06-12 | 2016-08-24 | 上海未泉新材料科技有限公司 | High-adhesion acrylic resin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627377A (en) * | 2018-12-12 | 2019-04-16 | 英德市雅家涂料有限公司 | A kind of ultrafast dry type automobile varnish hydroxy propylene acid resin and preparation method thereof |
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| Publication number | Publication date |
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| CN107573456B (en) | 2020-06-02 |
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Address after: 512000 Huacai chemical coating City, Wengcheng industrial transfer park, Wengyuan County, Shaoguan City, Guangdong Province Patentee after: Guangdong Di Aisheng Tongde Resin Co.,Ltd. Address before: 512627 Wengcheng Wengcheng industrial transfer park Huacai chemical coating City, Wengyuan County, Shaoguan City, Guangdong Province Patentee before: GUANGDONG TONGDE NEW MATERIAL CO.,LTD. |
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