CN101191041A - Acrylic ester adhesive - Google Patents
Acrylic ester adhesive Download PDFInfo
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- CN101191041A CN101191041A CNA2006101188738A CN200610118873A CN101191041A CN 101191041 A CN101191041 A CN 101191041A CN A2006101188738 A CNA2006101188738 A CN A2006101188738A CN 200610118873 A CN200610118873 A CN 200610118873A CN 101191041 A CN101191041 A CN 101191041A
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- acrylic ester
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- carbon
- ester adhesive
- aliphatic amide
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Abstract
The invention discloses an acrylate adhesive with stabilizer and a preparation method thereof. The stabilizer is added into the components of dual main-agent acrylate adhesive that comprises peroxide to ensure that storage stability of the component of the dual main-agent acrylate adhesive is good and the performances of the component of the dual main-agent acrylate adhesive such as shear strength, shock strength, positioning time, etc. are remained unchanged. The stabilizer of the acrylate adhesive is low-carbon aliphatic amine or comprises low-carbon aliphatic and metal chelating agent. The low-carbon aliphatic amine can postpone the polymerization of monomer, thus enhancing the storage stability of the acrylate adhesive. The low-carbon aliphatic amine is that alkyl, dialkyl or trialkyl substitutes the amine with the alkyl chain length from C2-C8, while the metal chelating agent is ethylene diamine tetraacetic acid (EDTA) and the salts thereof. The acrylate adhesive of the invention has good storage stability which can reach 360 h under 70 DEG C, without reducing the performances of shear strength, shock strength and positioning time, etc.
Description
Technical field
The present invention relates to a kind of acrylic ester adhesive technical field, particularly stablizer of acrylic ester adhesive and preparation method thereof.
Background technology
S-generation acrylic ester adhesive is made up of methacrylate monomer or performed polymer, elastomerics, initiator, promotor, stablizer etc., monomer, elastomerics, initiator, stablizer constitute a component, and monomer, elastomerics, promotor etc. are another component.Be divided into primary coat type and two types on two host types according to the method SGA that uses.
Two host type SGA claim mixed type, AB type again.Elastomerics is dissolved among the reactive acrylate monomer, adds stablizer, initiator etc. and be made into A agent (being called first component in the present invention).Be dissolved in the reactive acrylate monomer with elastomerics, add promotor, softening agent etc. and be made into B agent (being called second component in the present invention).A and B can be coated in respectively on the two adherend surfaces when bonding, just curable after superimposed.Gluing is bonding again after also A, B two component equal-volumes can being mixed.
Two host acrylic ester adhesives have the advantage of many uniquenesses: such as room temperature fast-curing; Substrate surface does not need strict the processing, even the greasy dirt face also can be bonding; Material that can be bonding is extensive; The bonding strength height; Applying glue is convenient, both manually actuatedly also can be used for automatic assembly line production.Therefore, acrylic ester adhesive is widely used in fields such as automobile, electromechanics, building and flight-line maintenance, also is widely used in the commercial market.
Yet because first component in two host acrylic ester adhesive contains superoxide, the slow initiating methacrylates monomer polymerization of superoxide meeting in storage process makes the viscosity of glue increase, even solidifies.If the envrionment temperature of transportation or storage will obviously be quickened the increase or the curing of glue viscosity than higher.Therefore, the stability in storage of raising acrylic ester adhesive is the problem that always receives publicity.
At present, the method for most both at home and abroad employing accelerated deterioration is estimated the stability in storage of acrylic ester adhesive, and the time length of accelerated deterioration shows that then the stability in storage of its room temperature is good.Nineteen eighty-three Hidemi Dohi has applied for using acetate, acrylate, methacrylate or its mixture of basic metal, zinc, the nickel stablizer patent (United States Patent (USP) 4 as acrylate adhesive, 403,058), 50 milliliters of glues are placed in 100 milliliters the polyethylene bottle aging down at 50 ℃, stability in storage increases with the consumption of stablizer, but performances such as shearing resistance, resistance to impact shock and setting time are with the consumption increase and the obviously decline of stablizer.50 ℃ of best digestion times is 30 days, but degradation 20-50% such as shearing resistance, resistance to impact shock and setting time.
People such as Samuel J.Chen are in nineteen ninety US patent 4,929, delivered a kind of acrylic ester adhesive stabilising system in 660, this system is made up of free radical polymerization inhibitor, metal-chelate mixture and radical scavenger, free radical polymerization inhibitor is the hydroquinine or derivatives thereof, and the metal-chelate mixture is α-An Jilinsuan or its an alkali metal salt, and radical scavenger is N, N one alkyl diaryl oxyamine or N, N one dialkyl group oxyamine.45 ℃ digestion times above one month.
People such as Ai De Germania were at patent (US in 1999,565,936) (ZL98109251.9) described a kind of method that improves the cruel tackiness agent stability in storage of vinylformic acid and in the patent in 2002, in containing the component of superoxide, add intercalating agent ethylenediamine tetraacetic acid (EDTA) di-ammonium salts, and, it is 10 days 50 ℃ digestion times 40 ℃ of-70 ℃ of heating.
Problem of above-mentioned prior art ubiquity is exactly still to fall short of the stable storing time.
Summary of the invention
Technical problem first aspect to be solved by this invention is to provide a kind of acrylic ester adhesive, this tackiness agent comprises stablizer, this stablizer joins in the component that contains superoxide of two host acrylic ester adhesives, can make this component have good stability in storage, property retentions such as two host acrylic ester adhesive shearing resistances, resistance to impact shock and the setting time of acquisition are constant.
Technical problem second aspect to be solved by this invention is to provide a kind of preparation method who comprises the acrylic ester adhesive of aforementioned stable agent.
As the acrylic ester adhesive of first aspect present invention, it comprises stablizer, and stablizer is formed by the low-carbon (LC) aliphatic amide or by low-carbon (LC) aliphatic amide and metal-chelate mixture.The low-carbon (LC) aliphatic amide has the effect that postpones monomer polymerization, thereby has strengthened the stability in storage of tackiness agent.
In the present invention, in the first per 100 parts component, the mass fraction of low-carbon (LC) aliphatic amide is 0.05-2.0.The mass fraction that preferred version of the present invention is the low-carbon (LC) aliphatic amide is 0.2-1.0, and at this moment the stabilising effect of acrylic ester adhesive is better.
In the present invention, the low-carbon (LC) aliphatic amide is used the better effects if of using separately than low-carbon (LC) aliphatic amide with the metal-chelate mixture.In the first per 100 parts component, the mass fraction of low-carbon (LC) aliphatic amide is 0.05-2.0, and the mass fraction of metal-chelate mixture is 0.001-0.1.Preferred version of the present invention is that the mass fraction of low-carbon (LC) aliphatic amide is 0.2-1.0 in per 100 parts first component, and the mass fraction of metal-chelate mixture is 0.005-0.06, and at this moment the stabilising effect of acrylic ester adhesive is better.
In the present invention, described low-carbon (LC) aliphatic amide be one two or trialkyl replace amine, its alkyl chain length is C2-C8.As be one or more mixture in monoethylamine, diethylamine, triethylamine, monoisopropylamine, Diisopropylamine, tri-isopropyl amine, a Tri N-Propyl Amine, di-n-propylamine, Tri-n-Propylamine, a n-Butyl Amine 99, Di-n-Butyl Amine, tri-n-butylamine, sec-butylamine, an isobutylamine, diisobutylamine, tri-isobutylamine, n-amylamine, cyclopentamine, normal hexyl Amine, an octodrine, two octodrines, a n-octyl amine, two n-octyl amine, the tri-n-octyl amine.
The metal-chelate mixture is ethylenediamine tetraacetic acid (EDTA) and its esters, as is one or more the mixture in disodium EDTA, ethylenediamine tetraacetic acid (EDTA) di-ammonium salts, tetrasodium salt of EDTA and ethylenediamine tetraacetic acid (EDTA) four ammonium salts.
Preparation method as the acrylic ester adhesive stablizer of second aspect present invention is: after preparing acrylic ester adhesive according to a conventional method, add the low-carbon (LC) aliphatic amide more while stirring in first component, stir 20min-30min at 20 ℃-35 ℃.
Second kind of preparation method as the acrylic ester adhesive stablizer of second aspect present invention is: after preparing acrylic ester adhesive according to a conventional method, in first component, add metal-chelate mixture and low-carbon (LC) aliphatic amide more while stirring, stir 20min-30min at 20 ℃-35 ℃.
In above-mentioned preparation method, the last adding of can pulverizing of metal-chelate mixture, also can be mixed with mass ratio with distilled water is to add behind 1: 2 the solution.
In per 100 part of first component, the add-on of metal-chelate mixture is 0.01 part-0.1 part, and the add-on of low-carbon (LC) aliphatic amide is 0.05 part-2 parts.When the add-on of metal-chelate mixture be the add-on of 0.005 part-0.06 part and low-carbon (LC) aliphatic amide when being 0.2 part-0.6 part stabilising effect better.
Acrylic ester adhesive stablizer of the present invention, add in the component that contains superoxide of acrylic ester adhesive, can obviously improve the stable storing performance of acrylic ester adhesive, its stability in storage in the time of 70 ℃ can reach 360h, and performances such as shearing resistance, resistance to impact shock and setting time do not descend yet.
Embodiment
In order to further specify effect of the present invention and method, now be illustrated with concrete embodiment.
Among the following embodiment, the test method of accelerated deterioration is: 40g first component is packed in the aluminum pipe of Φ 25mm * 140mm into sealing.Place 70 ℃ of baking ovens to be aged to the specified time, whether observe gel.
Embodiment
Embodiment 1: present embodiment table 1, table 2 have shown that employing low-carbon (LC) aliphatic amide stablizer of the present invention has obtained better stability in storage: sample A is for adopting low-carbon (LC) aliphatic amide stablizer of the present invention, sample B for do not adopt stablizer of the present invention in the same old way, setting time and tensile shear strength are sample A and second component in B and the table 1 are in the same old way solidified back mensuration.70 ℃ of storage stability test of B in the same old way are no more than 30h, and 70 ℃ of storage stability test of sample A reach 120h, the basic physical performance with significant difference is not taken place in B in the same old way, and also not decline of the shearing resistance after aging, prove that stabilising system of the present invention has excellent stability in storage.
Table 1
Table 2
Embodiment 2: present embodiment table 3, table 4 have shown that employing low-carbon (LC) aliphatic amide of the present invention and metal-chelate mixture stablizer have obtained better stability in storage: sample C is for adopting stablizer of the present invention, sample B for do not adopt stablizer of the present invention in the same old way, setting time and tensile shear strength are sample C and second component in B and the table 1 are in the same old way solidified back mensuration.70 ℃ of storage stability test of sample C reach 360h, the basic physical performance with significant difference is not taken place in B in the same old way, and the shearing resistance after aging do not descend yet, and proves that stabilising system of the present invention has excellent stability in storage.
Table 3
Table 4
Embodiment 3: the C among the embodiment 2 and domestic representational like product D, E, F have been carried out stability in storage relatively, and table 5 data show that 70 ℃ of stability in storagies of C obviously are better than like product.
Table 5
| Sample | C | D | E | F |
| 70 ℃ of stability in storagies (h) | 360 | 72 | 50 | 80 |
Embodiment 4: the sample G of present embodiment and H have used respectively than higher and lower tetrasodium salt of EDTA ratio, and 70 ℃ of stability in storagies were respectively 280 hours and 200 hours, significantly better than to B in the same old way.
Table 6
Embodiment 5: present embodiment has been tested 70 ℃ of stability in storagies of n-octyl amine in the low-carbon (LC) aliphatic amide, and 70 ℃ of stability in storagies that the data of table 7 show n-octyl amine are significantly better than to B in the same old way.
Table 7
The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (14)
1. an acrylic ester adhesive comprises stablizer, it is characterized in that, stablizer is the low-carbon (LC) aliphatic amide.
2. acrylic ester adhesive according to claim 1 is characterized in that, in per 100 parts of components that contain superoxide, the mass fraction of low-carbon (LC) aliphatic amide is 0.05-2.0.
3. acrylic ester adhesive according to claim 1 is characterized in that, in per 100 parts of components that contain superoxide, the mass fraction of low-carbon (LC) aliphatic amide is 0.2-1.0.
4. an acrylic ester adhesive comprises stablizer, it is characterized in that, stablizer is made up of low-carbon (LC) aliphatic amide and metal-chelate mixture.
5. acrylic ester adhesive according to claim 4 is characterized in that, in per 100 parts of components that contain superoxide, the mass fraction of low-carbon (LC) aliphatic amide is 0.05-2.0, and the mass fraction of metal-chelate mixture is 0.001-0.1.
6. acrylic ester adhesive according to claim 4 is characterized in that, in per 100 parts of components that contain superoxide, the mass fraction of low-carbon (LC) aliphatic amide is 0.2-1.0, and the mass fraction of metal-chelate mixture is 0.005-0.06.
7. according to the described acrylic ester adhesive of claim 1-6, it is characterized in that, described low-carbon (LC) aliphatic amide be one two or trialkyl replace amine, its alkyl chain length is C2-C8, as is monoethylamine, diethylamine, triethylamine, monoisopropylamine, Diisopropylamine, tri-isopropyl amine, one Tri N-Propyl Amine, di-n-propylamine, Tri-n-Propylamine, one n-Butyl Amine 99, Di-n-Butyl Amine, tri-n-butylamine, sec-butylamine, one isobutylamine, diisobutylamine, tri-isobutylamine, n-amylamine, cyclopentamine, normal hexyl Amine, one octodrine, two octodrines, one n-octyl amine, two n-octyl amine, the mixture of one or more in the tri-n-octyl amine.
8. according to the described acrylic ester adhesive of claim 4-6, it is characterized in that, described metal-chelate mixture is ethylenediamine tetraacetic acid (EDTA) and its esters, as is one or more the mixture in disodium EDTA, ethylenediamine tetraacetic acid (EDTA) di-ammonium salts, tetrasodium salt of EDTA and ethylenediamine tetraacetic acid (EDTA) four ammonium salts.
9. the preparation method of the described acrylic ester adhesive of claim 1, it is characterized in that: after preparing acrylic ester adhesive according to a conventional method, in the component that contains superoxide, add the low-carbon (LC) aliphatic amide more while stirring, stir 20min-30min at 20 ℃-35 ℃.
10. the preparation method of the described acrylic ester adhesive of claim 4, it is characterized in that: after preparing acrylic ester adhesive according to a conventional method, in the component that contains superoxide, add metal-chelate mixture and low-carbon (LC) aliphatic amide more while stirring, stir 20min-30min at 20 ℃-35 ℃.
11. preparation method according to claim 10 is characterized in that: the last adding of pulverizing of described metal-chelate mixture.
12. preparation method according to claim 10 is characterized in that: it is to add behind 1: 2 the solution that described metal-chelate mixture and distilled water are mixed with mass ratio.
13. according to the described preparation method of claim 10-12, it is characterized in that: in the per 100 parts components that contain superoxide, the add-on of metal-chelate mixture is 0.01 part-0.1 part, and the add-on of low-carbon (LC) aliphatic amide is 0.05 part-2 parts.
14. according to the described preparation method of claim 10-12, it is characterized in that: in the per 100 parts components that contain superoxide, the add-on of metal-chelate mixture is that the add-on of 0.005 part-0.06 part and low-carbon (LC) aliphatic amide is 0.2 part-0.6 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101188738A CN101191041B (en) | 2006-11-29 | 2006-11-29 | Acrylic ester adhesive |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101188738A CN101191041B (en) | 2006-11-29 | 2006-11-29 | Acrylic ester adhesive |
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| CN101191041A true CN101191041A (en) | 2008-06-04 |
| CN101191041B CN101191041B (en) | 2010-04-14 |
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| CN2006101188738A Active CN101191041B (en) | 2006-11-29 | 2006-11-29 | Acrylic ester adhesive |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023085409A1 (en) * | 2021-11-12 | 2023-05-19 | デンカ株式会社 | Adhesive tape and processing method |
| CN116731615A (en) * | 2023-06-08 | 2023-09-12 | 宁波鑫智达新材料有限公司 | Double-component acrylic adhesive and application thereof |
| WO2023188714A1 (en) * | 2022-03-31 | 2023-10-05 | デンカ株式会社 | Adhesive tape and processing method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057787C (en) * | 1996-11-15 | 2000-10-25 | 北京市天山新材料技术公司 | Anaerobic glue and preparation method |
| DE602005017472D1 (en) * | 2004-03-09 | 2009-12-17 | Henkel Corp | HEAT-CONDUCTIVE TWO-COMPONENT ADHESIVE COMPOSITION |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023085409A1 (en) * | 2021-11-12 | 2023-05-19 | デンカ株式会社 | Adhesive tape and processing method |
| WO2023188714A1 (en) * | 2022-03-31 | 2023-10-05 | デンカ株式会社 | Adhesive tape and processing method |
| CN116731615A (en) * | 2023-06-08 | 2023-09-12 | 宁波鑫智达新材料有限公司 | Double-component acrylic adhesive and application thereof |
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| CN101191041B (en) | 2010-04-14 |
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Owner name: SHANGHAI KANGDA CHEMICAL CO., LTD. Free format text: FORMER NAME: KANGDA CHEMICAL INDUSTRY CO., LTD., SHANGHAI |
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Address after: 169 Leizhou Road, Fengxian District, Shanghai, 201419 Patentee after: Kangda new material (Group) Co.,Ltd. Address before: 169 Leizhou Road, Fengxian District, Shanghai, 201419 Patentee before: Shanghai Kangda Chemical New Material Group Co.,Ltd. |
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