CN104356153B - A kind of adhesion promoter containing macromolecular photoinitiator and synthetic method thereof - Google Patents
A kind of adhesion promoter containing macromolecular photoinitiator and synthetic method thereof Download PDFInfo
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- CN104356153B CN104356153B CN201410469395.XA CN201410469395A CN104356153B CN 104356153 B CN104356153 B CN 104356153B CN 201410469395 A CN201410469395 A CN 201410469395A CN 104356153 B CN104356153 B CN 104356153B
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Abstract
The invention discloses a kind of adhesion promoter containing macromolecular photoinitiator and synthetic method thereof, this synthetic method is first in terms of mass fraction, in aqueous slkali, add 9 10 parts of epoxychloropropane and 22 24 parts of light trigger IHT PI 659, at room temperature react overnight, add the polyglycols of 20 40 parts, the catalyst of 0.1 0.3 parts, react at 100 DEG C 120 DEG C, purification of products, obtains macromolecular photoinitiator；46～66 parts of macromolecular photoinitiators and 9～12 parts of siloxanes adhesion promoters being dissolved in a solvent, be subsequently adding 12 20 parts of pyridines, reaction temperature is raised to 40 DEG C 80 DEG C, drip 13 15 parts of 1.3.5 benzene front three solution of acid chloride, after reaction, be cooled to room temperature, filter, solvent evaporated, obtains product；This adhesion promoter is good with the compatibility of resin, can overcome variable color yellowing, owing to there being polyglycols segment in molecule, reduces the internal stress of coating.
Description
Technical field
The present invention relates to a kind of adhesion promoter, particularly relate to a kind of adhesion promoter containing macromolecular photoinitiator and synthetic method thereof.This adhesion promoter belongs to ultraviolet light (UV) curing materials.
Background technology
Adhesion promoter can form stronger interaction with substrate surface and reach to strengthen the effect of adhesive force, it is usually containing multi-functional compound, active function groups is contained at its strand two ends, when resin is with ground effect, the functional group of one end and ground are by reaction strong bonded, this combination is typically direct strong with ground adhesion than coating, and other end functional group and the active group in coating react the firm chemical bond of formation, thus strengthen the adhesive force of coating and ground.Under ultraviolet light irradiates, light trigger is cracked to form rapidly free radical and causes the polyreaction of olefinic unsaturated-resin, in order to ensure light-cured resin, metallic substrate surface can there be is good adhesive force, the adhesion promoter of q.s, such as siloxanes, phosphoric acid ester adhesion promoter etc. must be added in formula.
But too much adhesion promoter can produce ill effect to the character of coating, α hydroxy-ketone micromolecular light trigger is received above adhesion promoter by chemical reaction by United States Patent (USP) US 8367743, the compound of synthesis can initiated polymerization, adhesive force can be promoted again, this compound adds the usage amount that can reduce adhesion promoter in formulation for coating material, it might even be possible to be not added with adhesion promoter.But the compound molecular weight of this synthesis is the highest, abnormal smells from the patient and volatility are of a relatively high, and resistance to migration is more weak, and meeting variable color yellowing when α hydroxy-ketone micromolecular light trigger is applied to ethylenically unsaturated monomer, oligomer forms high polymer, and affect its application.
Summary of the invention
In order to solve the problems referred to above, the invention discloses that a kind of mobility is low, the adhesion promoter containing macromolecular photoinitiator of invariant color yellowing and synthetic method thereof, apply the PASS of this adhesion promoter to reach 1 grade, pencil hardness reaches 1H.
The present invention is to receive in polyglycols macromole by little molecule light trigger, then organosiloxane and macromolecular photoinitiator is linked together with pyromellitic trimethylsilyl chloride.Macromolecular photoinitiator has many advantages, such as: the features such as abnormal smells from the patient is low, volatility is low, anti-migration ability is strong, environment compatibility good, good, the functional diversity of resin compatible, and macromolecular photoinitiator has certain effect for reducing yellowing.Two hydroxyls are contained at polyglycol molecules chain two ends, little molecule light trigger can be connected, prepare macromolecular photoinitiator, the macromole evocating agent prepared silane, phosphate ester adhesion promoter further with functional group reacts, the molecule of synthesis contains the adhesion promoter of macromolecular photoinitiator, disadvantage mentioned above may be overcome.This adhesion promoter volatility is low, and the compatibility with resin is good, can overcome variable color yellowing, owing to there being polyglycols segment in molecule, reduces the internal stress of coating.
The synthetic method of a kind of adhesion promoter containing macromolecular photoinitiator, is prepared by following steps:
1) in terms of mass fraction, in aqueous slkali, add 9 10 parts of epoxychloropropane and 22 24 parts of light trigger IHT PI 659, at room temperature react overnight, obtain product (epoxidised light trigger IHT PI 659)；
2) in terms of mass fraction, in step 1) products therefrom adds the polyglycols of 20 40 parts, the catalyst of 0.1 0.3 parts, react 1 hour 2 hours at 100 DEG C 120 DEG C, after completion of the reaction, product with diethyl ether purifies 1 time 5 times, remove responseless light trigger IHT PI 659, obtain macromolecular photoinitiator；Described catalyst is one or more in tetrabutyl ammonium bromide, tetraethylammonium bromide, chlorinating benzyl triethylamine, octadecyldimethyl ethylol amine nitrate, the double hexadecyldimethylamine ammonium of bromination and dodecyl dimethyl benzyl ammonium chloride；
3) in terms of mass fraction, 46～66 parts of described macromolecular photoinitiators and 9～12 parts of siloxanes adhesion promoters are dissolved in a solvent, it is subsequently adding 12 20 parts of pyridines, reaction temperature is raised to 40 DEG C 80 DEG C, and then 13 15 parts of 1.3.5 benzene front three solution of acid chloride of dropping, are stirred continuously lower reaction 20 minutes 60 minutes, it is cooled to room temperature, filter, solvent evaporated, obtain the adhesion promoter containing macromolecular photoinitiator；Described siloxanes adhesion promoter is 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl triethoxysilane, γ aminoethylaminopropyl trimethoxy silane, 3-aminopropyltriethoxy diethoxy silane.
Preferably, described polyglycols is one or more in Polyethylene Glycol, polypropylene glycol, poly-1.4 butanediols and poly-1.3 butanediols.
Preferably, described solvent is oxolane, acetone, chloroform, methyl ethyl ketone, 1.2 dimethoxy-ethanes or 1.4 dioxane.
Preferably, 1.3.5 benzene front three solution of acid chloride was added dropwise to complete in 5 minutes 20 minutes.
A kind of adhesion promoter containing macromolecular photoinitiator, is prepared by above-mentioned synthetic method.
Catalyst of the present invention is a kind of phase transfer catalyst.
Relative to prior art, the invention has the beneficial effects as follows: the present invention little molecule light trigger is under the effect of catalyst and polyglycols reaction prepares macromolecular photoinitiator, then with pyromellitic trimethylsilyl chloride, organosiloxane and macromolecular photoinitiator are linked together, prepare the adhesion promoter containing macromolecular photoinitiator.Containing photoinitiator moiety in this adhesion promoter, resin polymerization can be caused as light trigger, and polyglycols is connected with photoinitiator moiety, improves molecular weight, the animal migration after reducing the volatility of light trigger and solidifying；This adhesion promoter is good with the compatibility of resin, can overcome variable color yellowing, owing to there being polyglycols segment in molecule, reduces the internal stress of coating.
Detailed description of the invention
For being more fully understood that the present invention, below in conjunction with embodiment, the invention will be further described, it should be noted that embodiment does not constitute limiting the scope of the present invention.
Embodiment 1:
With polyethylene glycol 200, light trigger IHT PI 659 (English power science and technology), 3-aminopropyl trimethoxysilane is raw material.
The synthetic method of a kind of adhesion promoter containing macromolecular photoinitiator, is prepared by following steps:
A) 16.3g sodium hydroxide and 0.76g 4-butyl ammonium hydrogen sulfate are dissolved in 45ml water, ice-water bath cools down 20 minutes, add 24.0g epoxychloropropane, 10.32g is dissolved in the light trigger IHT PI 659 of 1.2 dimethoxy-ethanes of 95ml, react overnight under mixture room temperature, isolate water layer, obtain organic layer, remove solvent and obtain product；
B) during 8.00g polyethylene glycol 200 is dissolved in 20ml acetone, add 0.06g tetrabutyl ammonium bromide, it is warming up to 120 DEG C, is slowly added dropwise the product with the step a) of 10ml acetone solution, is stirred continuously, 120 DEG C are reacted 1.5 hours, reacting complete, rotation is evaporated off solvent, product with diethyl ether purification by liquid extraction 3 times, remove unreacted light trigger IHT PI 659, obtain product.
C) the 3-aminopropyl trimethoxysilane of the product in step b), 2.68g is dissolved in 25ml oxolane, it is subsequently adding 3.72g pyridine, reaction temperature is slowly raised to 60 DEG C, then in 20 minutes, slowly drip off 3.99g be dissolved in the 1.3.5 benzene front three solution of acid chloride of 20ml oxolane, it is stirred continuously lower reaction 60 minutes, is cooled to room temperature, filter, solvent evaporated, obtains the 18.96g adhesion promoter containing macromolecular photoinitiator.
Embodiment 2:
With PEG400, light trigger IHT PI 659 (English power science and technology), 3-aminopropyl triethoxysilane (KH 550) is raw material.
The synthetic method of a kind of adhesion promoter containing macromolecular photoinitiator, is prepared by following steps:
A) 16.3g sodium hydroxide and 0.76g 4-butyl ammonium hydrogen sulfate are dissolved in 45ml water, ice-water bath cools down 20 minutes, add 24.0g epoxychloropropane, 10.32g is dissolved in the light trigger IHT PI 659 of 95ml1.2 dimethoxy-ethane, react overnight under mixture room temperature, isolate water layer, obtain organic layer, remove solvent and obtain product；
B) during 16.00g PEG400 is dissolved in 20ml acetone, add 0.04g tetrabutyl ammonium bromide, it is warming up to 110 DEG C, is slowly added dropwise the product by a) step of 10ml acetone solution, is stirred continuously, 110 DEG C are reacted 2 hours, reacting complete, rotation is evaporated off solvent, product with diethyl ether purification by liquid extraction 3 times, remove unreacted light trigger IHT PI 659, obtain product.
C) product in b) step, 3.31g3-aminopropyl triethoxysilane are dissolved in 25ml oxolane, it is subsequently adding 3.72g pyridine, reaction temperature is slowly raised to 70 DEG C, then in 20 minutes, slowly drip off 3.99g be dissolved in the 1.3.5 benzene front three solution of acid chloride of 20ml oxolane, it is stirred continuously lower reaction 40 minutes, is cooled to room temperature, filter, solvent evaporated, obtains the 30.89g adhesion promoter containing macromolecular photoinitiator.
Embodiment 3:
With polypropylene glycol 200, light trigger IHT PI 659 (English power science and technology), γ aminoethylaminopropyl trimethoxy silane (KH792) is raw material.
The synthetic method of a kind of adhesion promoter containing macromolecular photoinitiator, is prepared by following steps:
A) 16.3g sodium hydroxide and 0.76g 4-butyl ammonium hydrogen sulfate are dissolved in 45ml water, ice-water bath cools down 20 minutes, add 24.0g epoxychloropropane, 10.32g is dissolved in the light trigger IHT PI 659 of 95ml1.2 dimethoxy-ethane, react overnight under mixture room temperature, isolate water layer, obtain organic layer, remove solvent and obtain product；
B) during 8.00g polypropylene glycol 200 is dissolved in 20ml acetone, add 0.05g tetrabutyl ammonium bromide, it is warming up to 115 DEG C, is slowly added dropwise the product by a) step of 10ml acetone solution, is stirred continuously, 115 DEG C are reacted 2.0 hours, reacting complete, rotation is evaporated off solvent, product with diethyl ether purification by liquid extraction 3 times, remove unreacted light trigger IHT PI 659, obtain 18.93g macromolecular photoinitiator.
C) product in b) step, 3.33gKH 792 are dissolved in 25ml oxolane, it is subsequently adding 3.72g pyridine, reaction temperature is slowly raised to 60 DEG C, then in 20 minutes, slowly drip off 3.99g be dissolved in the 1.3.5 benzene front three solution of acid chloride of 20ml oxolane, it is stirred continuously lower reaction 60 minutes, is cooled to room temperature, filter, solvent evaporated, obtains the 19.61g adhesion promoter containing macromolecular photoinitiator.
Embodiment 4:
With polypropylene glycol 400, light trigger IHT PI 659 (English power science and technology), 3-aminopropyltriethoxy diethoxy silane (KH902) is raw material.
The synthetic method of a kind of adhesion promoter containing macromolecular photoinitiator, is prepared by following steps:
A) 16.3g sodium hydroxide and 0.76g 4-butyl ammonium hydrogen sulfate are dissolved in 45ml water, ice-water bath cools down 20 minutes, add 24.0g epoxychloropropane, 10.32g is dissolved in the light trigger IHT PI 659 of 95ml1.2 dimethoxy-ethane, react overnight under mixture room temperature, isolate water layer, obtain organic layer, remove solvent and obtain product；
B) during 16.00g polypropylene glycol 400 is dissolved in 20ml acetone, add 0.04g tetrabutyl ammonium bromide, it is warming up to 120 DEG C, is slowly added dropwise the product by a) step of 10ml acetone solution, is stirred continuously, 120 DEG C are reacted 2 hours, reacting complete, rotation is evaporated off solvent, product with diethyl ether purification by liquid extraction 3 times, remove unreacted light trigger IHT PI 659, obtain 27.44g macromolecular photoinitiator.
C) product in b) step, 3.07gKH 902 are dissolved in 25ml oxolane, it is subsequently adding 3.72g pyridine, reaction temperature is slowly raised to 70 DEG C, then in 20 minutes, slowly drip off 3.99g be dissolved in the 1.3.5 benzene front three solution of acid chloride of 20ml oxolane, it is stirred continuously lower reaction 40 minutes, is cooled to room temperature, filter, solvent evaporated, obtains the 30.67g adhesion promoter containing macromolecular photoinitiator.
For proving that the product of above-described embodiment gained can be as adhesion promoter, it is provided that Application Example below.The synthetic method of Application Example is to mix according to table 1 formula in universal paint preparation.
Application Example
By the adhesion promoter containing macromolecular photoinitiator of preparation in embodiment 14, paint by preparing such as the formula of table 1 below:
Table 1
By raw material mix homogeneously in table, being coated on electroplating steel plate, thickness is 25 ± 5um, then UV solidification, and energy is more than 500mJ/cm2, then its performance is tested.Adhesion test method is GB/T1720 1979, and measurement of luster method is GB 1,743 1979, and hardness measuring method is GB/T6739 2006.
Test result is as shown in table 2.
Table 2
| Matched group 1 | Matched group 2 | Application examples 1 | Application examples 2 | Application examples 3 | Application examples 4 | |
| Adhesive force (method of drawing a circle) | 2 grades | 2 grades | 1 grade | 1 grade | 1 grade | 1 grade |
| Glossiness | 88 | 87 | 89 | 88 | 87 | 88 |
| Hardness (Pencil scratch) | 1H | F | 1H | 1H | 1H | 1H |
From the point of view of test result by table 2, adhesive force in application examples 14 all big than matched group 12, owing to matched group 1 not adding adhesion promoter, obviously little than other of its adhesive force, although matched group 2 with the addition of adhesion promoter KH 550, and its light-initiated dosage added is identical with application examples 14, but the adhesion promoter containing macromolecular photoinitiator added in 14 in application examples, this adhesion promoter can cause photopolymerization, so film curing in application examples 14 is more complete, so big than matched group 2 of its adhesive force；The hardness matched group 1 of paint film is identical with application examples 14, all big than matched group 2, application examples 14 introduces polyglycols soft chain segment and phenyl ring rigid chain segment, two results interacted make hardness of paint film change little, and matched group 2 is due to solidification not exclusively, the molecular weight of paint film is little, so hardness is less.In sum, the use of the adhesion promoter containing macromolecular photoinitiator so that the consumption needing the little molecule light trigger of addition in formula is less, can alleviate the shortcoming that little molecule light trigger brings, and not make the glossiness of paint film decline.And, containing photoinitiator moiety in the adhesion promoter of the present invention, resin polymerization can be caused as light trigger, and polyglycols is connected with photoinitiator moiety, improves molecular weight, the animal migration after reducing the volatility of light trigger and solidifying；This adhesion promoter is good with the compatibility of resin, can overcome variable color yellowing, owing to there being polyglycols segment in molecule, reduces the internal stress of coating.
Claims (5)
1. the synthetic method of the adhesion promoter containing macromolecular photoinitiator, it is characterised in that prepared by following steps:
1) in terms of mass fraction, in aqueous slkali, 9 10 parts of epoxychloropropane and 22 24 parts of light trigger IHT PI 659 are added,
At room temperature react overnight, obtain product；
2) in terms of mass fraction, in step 1) products therefrom adds the polyglycols of 20 40 parts, the catalyst of 0.1 0.3 parts,
Reacting at 100 DEG C 120 DEG C 1 hour 2 hours, after completion of the reaction, product with diethyl ether purifies 1 time 5 times, and removing does not has
The light trigger IHT PI 659 of reaction, obtains macromolecular photoinitiator；Described catalyst is tetrabutyl ammonium bromide, tetrem bromide
Change ammonium, chlorinating benzyl triethylamine, octadecyldimethyl ethylol amine nitrate, the double hexadecyldimethylamine ammonium of bromination and chlorination
One or more in dodecyl dimethyl hexadecyldimethyl benzyl ammonium；
3) in terms of mass fraction, 46～66 parts of described macromolecular photoinitiators and 9～12 parts of siloxanes adhesive force are promoted
Agent is dissolved in a solvent, is subsequently adding 12 20 parts of pyridines, and reaction temperature is raised to 40 DEG C 80 DEG C, then dropping 13 15 part 1,3,5
Benzene front three solution of acid chloride, is stirred continuously lower reaction 20 minutes 60 minutes, is cooled to room temperature, filters, solvent evaporated, obtains
Adhesion promoter containing macromolecular photoinitiator；Described siloxanes adhesion promoter be 3-aminopropyl trimethoxysilane,
3-aminopropyl triethoxysilane, γ aminoethylaminopropyl trimethoxy silane, 3-aminopropyltriethoxy diethoxy silane.
The synthetic method of the adhesion promoter containing macromolecular photoinitiator the most according to claim 1, it is characterised in that
Described polyglycols is one or more in Polyethylene Glycol, polypropylene glycol, poly-1,4 butanediols and poly-1,3 butanediols.
The synthetic method of the adhesion promoter containing macromolecular photoinitiator the most according to claim 1, it is characterised in that
Described solvent is oxolane, acetone, chloroform, methyl ethyl ketone, 1,2 dimethoxy-ethanes or 1,4 dioxane.
The synthetic method of the adhesion promoter containing macromolecular photoinitiator the most according to claim 1, it is characterised in that
1,3,5 benzene front three solution of acid chloride were added dropwise to complete in 5 minutes 20 minutes.
5. the adhesion promoter containing macromolecular photoinitiator, it is characterised in that it is by described in any one of claim 14
Synthetic method prepares.
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| CN110746523B (en) * | 2018-07-23 | 2021-07-27 | 中国科学院理化技术研究所 | Lignin-based macromolecular photoinitiator and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102232081A (en) * | 2008-12-01 | 2011-11-02 | 巴斯夫欧洲公司 | Silsesquioxane photoinitiators |
| US8367743B2 (en) * | 2007-10-17 | 2013-02-05 | Basf Se | Adhesion promoting photoinitiators for UV cured coatings over metal surfaces |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8367743B2 (en) * | 2007-10-17 | 2013-02-05 | Basf Se | Adhesion promoting photoinitiators for UV cured coatings over metal surfaces |
| CN102232081A (en) * | 2008-12-01 | 2011-11-02 | 巴斯夫欧洲公司 | Silsesquioxane photoinitiators |
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| Title |
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| 光引发剂的新进展;聂俊;《2006全国辐射固化研讨会论文集》;20070822;第92-98页 * |
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Effective date of registration: 20180716 Address after: 519040 Zhuhai, Guangdong, Jin Wan District, San Zao Town, 113 Patentee after: Tianda Polytron Technologies Inc Address before: 510640 No. five, 381 mountain road, Guangzhou, Guangdong, Tianhe District Patentee before: South China University of Technology |