CN1718567A - Acrylate kind oligomer with side chain containing unsaturated functional group, its proparation method and light solidifying paint composition containing same - Google Patents
Acrylate kind oligomer with side chain containing unsaturated functional group, its proparation method and light solidifying paint composition containing same Download PDFInfo
- Publication number
- CN1718567A CN1718567A CN 200410069104 CN200410069104A CN1718567A CN 1718567 A CN1718567 A CN 1718567A CN 200410069104 CN200410069104 CN 200410069104 CN 200410069104 A CN200410069104 A CN 200410069104A CN 1718567 A CN1718567 A CN 1718567A
- Authority
- CN
- China
- Prior art keywords
- coo
- reaction
- oligopolymer
- formula
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
Abstract
An acrylate-type oligomer containing unsaturated radicals in its side chain, its preparing process and its application for preparing the optically solidified paint ink, adhesive, etc with high solidifying speed are disclosed.
Description
Technical field
The present invention relates to a class new can contain the particularly origoester acrylate and preparation method thereof of the two keys of C=C of multiple functional group at side chain.The invention still further relates to the light solidifying paint composition that comprises aforesaid propylene esters of gallic acid oligopolymer.
Background technology
Photocuring technology is a kind of green technology in the fields such as coating, printing ink, tackiness agent; its body of material generally is made up of the resin that contains acryl and polyalcohol acrylate and light trigger; under enough luminous energy (for example ultraviolet ray or visible light) effects, all solidify.Compare with traditional solvent system that contains, it has solvent-free discharging, efficient height, outstanding feature such as energy-conservation, is applied in various fields.Photo-cured coating, printing ink, tackiness agent etc. are by the decision of its composition, and oligopolymer needs at least one to contain, and the polymeric unsaturated functional group can take place under illumination condition, the at present common acryl that mostly is.Be usually used in the light initiation polymerization that oligopolymer in the industry such as photo-cured coating, printing ink can be divided into unsaturated polyester, acrylic acid or the like oligopolymer, Resins, epoxy, other systems such as mercaptan and vinyl monomer.Wherein the acrylic acid or the like oligopolymer is because its good stability to hydrolysis and light stability, and laser curing velocity is fast, thereby is widely used in the photocuring system.But common oligopolymer mainly is meant the oligopolymer that contains Resins, epoxy, urethane, polyester and silicone resin that the acryl structural unit is an end group at present; the oligopolymer of the two keys of side chain band C=C is rare; because the double bond conversion rate of photopolymer has only about 80%; so oligopolymer with two or three activity double keys; often effect is bad, is difficult to the mechanical strength that reaches required.
JP-A-01-153703 has disclosed a kind of by α, and the esterification of β-carboxylic acid anhydride-double bond compound inserts the method for unsaturated compound, because the viscosity of Resins, epoxy is big, makes polymerization need high temperature or adding solvent, can cause polymerization again in heat-processed.
Defective according to prior art, if in side chain, introduce the two keys of active C=C, prepare the more activity double keys of having of novel structure, the more low viscosity of high reaction activity, pure acrylic acid esters resin cheaply, to have wide practical use, can better solve the surface attachment of various base materials and the contraction problem that comes off.
At the deficiencies in the prior art, the inventor has carried out intensive research, found that the present invention describes contain unsaturated functional group particularly the esters of acrylic acid oligomer compounds of the two keys of C=C have good performance, and can be according to the needs of Application Areas requirement, add different diluting monomers (as TMPTA, HDDA, NPGDA, TPGDA, BDDA etc.) performance is allocated.Modulate the low viscous acrylate quasi-oligomer that just can prepare the unsaturated functional group that contains different numbers as required by simple transesterification reaction with proportioning.Monomer complexes such as TMPATA, NPGDA, TPGDA, HDDA become the photo-cured coating of various excellent performances easily, so finished the present invention.
Summary of the invention
The purpose of this invention is to provide the new side chain of a class and contain the particularly acrylate quasi-oligomer of C=C functional group of unsaturated functional group.
Another object of the present invention provides the preparation method that side chain contains unsaturated functional group acrylate quasi-oligomer.
A further object of the present invention provides a class and comprises the above-mentioned light solidifying paint composition that contains the acrylate quasi-oligomer of unsaturated functional group.
Another object of the present invention is the application that described side chain contains C=C double bond functional group's acrylate quasi-oligomer.
Specifically, the invention provides the acrylate quasi-oligomer that a kind of side chain contains unsaturated functional group, its structural formula is as follows:
Wherein,
A is a carbalkoxy, for example, and-COOR
1, R wherein
1Be C
1～C
6Aliphatic alkyl or phenyl, preferably C
1～C
4Aliphatic alkyl;
B is the dibasic alcohol ester group, for example, and-COO (CH
2CH
2O)
nH ,-COO (CH
2)
nOH;
C is the carboxylic acid ester groups that contains the two keys of C=C, for example, and-COO (CH
2)
nOCOCH=CHCOOH ,-COO (CH
2CH
2O)
nCOCH=CH
2COOH;
D is the ester group that contains the two keys of C=C, for example, and-COO (CH
2)
nOCOCH=CH
2,-COO (CH
2) nOCOC (R)=CH
2,-COO (CH
2CH
2O) nCOCH=CH
2,-COO (CH
2CH
2O) nCOC (R)=CH
2, wherein, R is methyl or ethyl;
m
1Be 1～20 integer, preferably 2～10; m
2And m
3Be respectively 0～10 integer independently, be preferably 1～5; m
2And m
3Can not be 0 simultaneously; m
1+ m
2+ m
3=3～60, preferably 5～15;
n
1, n
2, n
3And n
4Be respectively 1～150 integer independently, preferably 5～30;
n
1+ n
2+ n
3+ n
4=4～150, preferably 20～40;
N is 1～20 integer, preferably 2～5.
Generally speaking, the number-average molecular weight of formula of the present invention (I) oligopolymer is 1,000～5,000, preferably 2,000～3,000.
Formula of the present invention (I) oligopolymer can adopt for example following step preparation:
The two optional one or whole,
Wherein,
R
1Be C
1～C
6Fat alkane family's base (for example methyl, ethyl or propyl group) or phenyl;
R
2Be C
2～C
8Dibasic alcohol or condensation glycol ether, as HO (CH
2CH
2O)
nH, HO (CH
2)
nOH, n are 1～8 integers, preferably 1～4;
R
3Being the carboxylicesters that contains the two keys of C=C, for example, can be TMPTA (Viscoat 295), CH
2=CHCOOR
1(acrylate), CH
2=C (CH
3) COOR
1(methacrylic ester), EO
3-TMPTA (ethoxylation (3) Viscoat 295), PO
3-TMPTA (propoxylation Viscoat 295), PHEA (benzene oxygen ethyl propylene acid esters), PETA (pentaerythritol triacrylate), TPGDA (tripropylene glycol diacrylate), DPGDA (propylene glycol diacrylate), NPGDA (neopentylglycol diacrylate), PO
2-NPGDA (propoxylation (2) neopentylglycol diacrylate), HDDA (1,6 hexanediol diacrylate), PDDA (PDDA), BDDA (1,4 butanediol diacrylate), PO
3-GTA (propoxylation (3) glycerol tri-acrylate), PDTPDA (phthalic acid tripropylene glycol diacrylate), EO
4BPDA (ethoxylation (4) bisphenol a diacrylate), LA (dodecyl acrylate), SMA (methacrylic dodecyl gallate), PUA (urethane acrylate), PEA (polyester acrylate), PEG (200) DA (polyoxyethylene glycol (200) diacrylate), EOEOEA (ethoxy ethoxy ethyl propylene acid esters) etc.; Preferred acrylate, methacrylic ester, TMPTA, TPGDA, HDDA, BDDA etc.
R
4Be the C that contains two keys
4～C
5Dicarboxylic anhydride (as MALEIC ANHYDRIDE);
A is a carbalkoxy, for example, and-COOR
1, R wherein
1Be C
1～C
6Aliphatic alkyl or phenyl, preferably C
1～C
4Aliphatic alkyl;
B is the dibasic alcohol ester group, for example, and-COO (CH
2CH
2O)
nH ,-COO (CH
2)
nOH;
C is the carboxylic acid ester groups that contains the two keys of C=C, for example, and-COO (CH
2)
nOCOCH=CHCOOH ,-COO (CH
2CH
2O)
nCOCH=CH
2COOH;
D is the ester group that contains the two keys of C=C, for example, and-COO (CH
2)
nOCOCH=CH
2,-COO (CH
2) nOCOC (R)=CH
2,-COO (CH
2CH
2O) nCOCH=CH
2,-COO (CH
2CH
2O)
nCOC (R)=CH
2, wherein, R is methyl or ethyl;
n
1, n
2, n
3And n
4Be respectively 1～150 integer independently, preferably 5～30;
n
1+ n
2+ n
3+ n
4=4～150, preferably 20～40;
N is 1～20 integer, preferably 2～5.
m
1Be 1～20 integer, preferably 2～10; m
2And m
3Be respectively 0～10 integer independently, be preferably 1～5; m
2And m
3Can not be 0 simultaneously; m
1+ m
2+ m
3=3～60, preferably 5～15;
Cat
1Can be initiator, chain-transfer agent or solvent, the polymerization degree of molecule can be under the polymer polymerizing processing condition, and at initiator, chain-transfer agent and solvent action are convenient down to be obtained.
Described initiator, chain-transfer agent or solvent can adopt commonly used those in this area, and for example initiator can be Diisopropyl azodicarboxylate (AIBN), dibenzoyl peroxide (BPO), dicumyl peroxide (DCP) etc.; Chain-transfer agent can be thiomethyl alcohol, Virahol, lauryl mercaptan etc.; Solvent can be benzene, toluene, hexanaphthene, 1,2-ethylene dichloride, ethyl acetate, butylacetate, ethanol etc.
Cat
2Can be any transesterification catalyst that is suitable for the inventive method, as Base or H
+, wherein, Base is C
1-C
6Sodium alkyl alcohol, C
1-C
6Alkyl potassium alcoholate, sodium hydroxide, potassium hydroxide, sodium Metal 99.5 etc., particular methanol sodium, sodium ethylate, sodium Metal 99.5; H
+Be Lewis acid or protonic acid;
Cat
3Can be any transesterification catalyst that is suitable for the inventive method, as Base or H
+, wherein, Base is C
1-C
6Sodium alkyl alcohol, C
1-C
6Alkyl potassium alcoholate, sodium hydroxide, potassium hydroxide, sodium Metal 99.5 etc., particular methanol sodium, sodium ethylate, sodium Metal 99.5 etc.; H
+Be Lewis acid or protonic acid.
Cat
2And Cat
3Can be identical or different, preferably identical.
Formula of the present invention (I) oligopolymer can adopt conventional polymerization technique preparation, and for example, 4 steps in above-mentioned preparation formula of the present invention (I) the oligopolymer method can adopt following processing condition:
Step 1, polyacrylate(s) synthetic: with the acrylic ester monomer is raw material, adds Cat
1Initiator, solvent and chain-transfer agent, temperature of reaction are controlled at 35～120 ℃, and preferred 60～90 ℃, fully stirring reaction obtains product M1;
Step 2 is with M1 and R
2Dibasic alcohol or condensation glycol ether reaction, M1 and R
2Material proportion be 1～8: 1, preferred 3～5: 1, add Base or H
+Catalyzer, its temperature of reaction are controlled at 45～150 ℃, and preferred 60～100 ℃, fully stirring reaction obtains product M2;
The two selects one or whole following steps,
Step 3 is with M2 and R
3The carboxylicesters reaction that contains the two keys of C=C, M2 and R
3Material proportion be 1～8: 1, preferred 3～5: 1, add Base or H
+Catalyzer, its stable reaction are controlled at 30～120 ℃, and preferred 50～80 ℃, fully stirring reaction obtains product M3, and catalyzer is preferably identical with step 2.
Step 4 is with M2 or M3 and R
4Unsaturated dicarboxylic acid anhydride reaction, its temperature of reaction is controlled at 30～100 ℃, preferred 50～90 ℃, fully stirring reaction obtains target product I, formula promptly of the present invention (I) oligopolymer.
Its condition is to work as m
2Or m
3Be 0 o'clock, the inventive method does not comprise step 3 or step 4.In other words, work as m
2Be 0 o'clock, the inventive method does not comprise step 4, and promptly M3 is formula of the present invention (I) oligopolymer; Work as m
3Be 0 o'clock, the inventive method does not comprise step 3, promptly adopts M2 and R
4Direct reaction obtains formula of the present invention (I) oligopolymer.
Preparation polymerization process that oligopolymer of the present invention adopts is well known in the art, and for example acrylate is made initiator, thiomethyl alcohol or Virahol at Diisopropyl azodicarboxylate and done that polymerization obtains polyacrylic ester under the condition of chain-transfer agent.Use alcohol (methyl alcohol or ethanol) to obtain controlled lower molecular weight, low viscous polymkeric substance in the present invention as solvent.
For the present invention, transesterify desired raw material resin should be the oligopolymer with certain polymerization degree that contains side chain ester group or hydroxyl at least, their available methods of knowing usually are synthetic, for example, acrylate or hydroxy acrylate and other monomer are polymerized according to a certain percentage, common available thiomethyl alcohol or lauryl mercaptan are made chain-transfer agent, regulate molecular weight with ethanol as solvent, make polymerization starter with Diisopropyl azodicarboxylate.
Formula of the present invention (I) oligopolymer can get the modification intermediate with different alcohol (monohydroxy-alcohol, dibasic alcohol or its polymkeric substance) by ester-interchange method with the polyacrylic ester of certain molecular weight, carries out transesterify with various double bond containing esters again and obtains.It is included in the gained ester interchange intermixture, can use without separating directly.
Formula of the present invention (I) oligopolymer can also carry out transesterify with various double bond containing esters and obtain by the acrylate monomer direct polymerization of hydroxyl again.
The present invention also provides a class to include the light solidifying paint composition of described oligopolymer.Mixing obtained light solidifying paint composition after the diluting monomer (as: TMPTA, HDDA, TPGDA etc.) that requires to have dissolved light trigger according to purposes added formula of the present invention (I) oligopolymer.Composition and weight ratio thereof contained in the described composition are formula (I) oligopolymer: light trigger: auxiliary agent: diluting monomer is 1.000: 0.010-0.100: 0.002-0.100: 0.100-10.000, preferably 1.000: 0.020-0.050: 0.010-0.050: 0.500-3.000.
Oligopolymer in the above-mentioned light solidifying paint composition is formula of the present invention (I) oligopolymer; Light trigger can adopt 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide (TPO), 1-hydroxy-cyclohexyl phenyl ketone (184), 2-methyl-2-hydroxyl-1-phenyl-1-acetone (1173), 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone (907), 2-isopropyl thioxanthone (ITX); Auxiliary agent comprises defoamer, flow agent, mould inhibitor, dispersion moisture agent etc.; Diluting monomer can be selected vinylbenzene, butyl acrylate, bifunctional monomer such as tripropylene glycol diacrylate, 1 for use according to different purposes and requirement, the 3-butylene glycol diacrylate, active monomer of polyfunctional group such as Viscoat 295, pentaerythritol triacrylate, PDDA, 1,4 butanediol diacrylate or phthalic acid three propanedioic acid diacrylates etc.
Acrylic resin of the present invention has excellent photostabilization, weathering resistance, and look shallow, and water-white is transparent, and erosion resistance is strong, and monomer is extensive, can carry out reasonably combinedly according to performance requriements, has the reactivity of minimum pigment.Resin of the present invention (promptly, acrylate quasi-oligomer of the present invention) except that advantage with acrylic resin itself, when being used to prepare visible-light curing coating, also having high molecular and distribute and to be tending towards evenly, not have smell, film performance good, characteristics such as solvent-free pollution.
Acrylic resin of the present invention is because side chain contains the two keys of C=C, can form super macromole behind the photocuring, thereby have good mechanical performance (as toughness, sticking power, hardness etc.), and favorable chemical resistance energy (as water tolerance, resistance to acids and bases, salt fog resistance, solvent resistance etc.).Acrylic resin of the present invention has good adhesive on the polar substrates surface, and for example strong adhesion on the base materials such as metal, stone material, plastics, woodenware can reach 0～1 grade.The present invention can effectively regulate performances such as the hardness, plasticity, increasing tougheness, weathering resistance, erosion resistance of resin by modified side chain.Therefore, the invention provides the preparation method of the resin of a kind of low polymerization degree, low viscosity, high reactivity, low cost, many performances.
Acrylic resin of the present invention is direct initiated polymerization also, also can with other reactive monomer or the composite use of resin, thereby successfully solved traditional photo-cured coating resin viscosity big, need add reactive monomer or solvent viscosity reduction and be beneficial to construction and cause that film shrinks, and the puzzlement of toughness, sticking power, glossiness, hardness, poor performance such as wear-resisting, can be widely used in various UV light sources, systems such as visible light source and day photocuring also can be mixed with the photocuring aqueous latex paint and use.
Resin of the present invention has the excellent properties of common acrylic resin, can be widely used in preparing in the photocuring systems such as photo-cured coating, printing ink, photocuring paper.At metal, scleroproein surface, stone material, frosting extensive use is arranged all.The photo-cured coating of preparing with modified resin of the present invention has that curing speed is fast, cost is low, the film performance excellent characteristics of formation.
Embodiment
The present invention can be further described with indefiniteness embodiment hereinafter.
Embodiment 1: the preparation of lower molecular weight, low viscous polymkeric substance
Take by weighing methyl acrylate 500g, ethanol 180g, Diisopropyl azodicarboxylate 5.0g, lauryl mercaptan 25.0g mix mixture A.In the 2000mL there-necked flask of a band stirring and reflux exchanger, add ethanol 320g, be warming up to 80 ℃, mixture A is dropped in the there-necked flask, controlled temperature is 70～90 ℃ in the process, 3h dropwises, the insulation 4h that continue to reflux, be cooled to 40 ℃ after, the decompression precipitation, thus polymkeric substance (M1) obtained.
The number-average molecular weight 2,500～3,000 of polymkeric substance M1, viscosity 8,000～9,000 centipoise.
Embodiment 2: the preparation of lower molecular weight, low viscous polymkeric substance
Take by weighing methyl acrylate 250g, methyl methacrylate 250g, hexanaphthene 180g, dibenzoyl peroxide (BPO) 5.0g, lauryl mercaptan 25.0g mix and obtain mixture A '.In the 2000mL there-necked flask of a band stirring and reflux exchanger, add hexanaphthene 320g, be warming up to 80 ℃, mixture A ' is dropped in the there-necked flask, controlled temperature is 70～90 ℃ in the process, 3h dropwises, the insulation 4h that continue to reflux, be cooled to 40 ℃ after, the decompression precipitation, thus polymkeric substance (M1) obtained.
The number-average molecular weight 2,500～3,000 of polymkeric substance M1, viscosity 8,000～9,000 centipoise.
Embodiment 3: side chain contains the preparation of unsaturated functional group acrylate quasi-oligomer
In the 250mL there-necked flask of a band stirring and reflux exchanger, add 60g embodiment 1 or embodiment 2 resulting polymers M1, take by weighing sodium methylate 1g and add wherein, the back that stirs adds glycol ether 10g, is warming up to 70～80 ℃, abundant stirring reaction 3～4h, the decompression precipitation adds TMPTA30g subsequently, continues to add behind 70～80 ℃ of abundant stirring reaction 4h MALEIC ANHYDRIDE 3g, temperature is controlled at 70～80 ℃, continues reaction 2h and promptly obtains oligopolymer of the present invention (I).
The number-average molecular weight 2,500～3,500 of formula (I), viscosity 8,000～9,000 centipoise.
Embodiment 4: side chain closes the preparation of unsaturated functional group acrylate quasi-oligomer
In the 250mL there-necked flask of a band stirring and reflux exchanger, add 60g embodiment 1 or embodiment 2 resulting polymers M1, take by weighing sodium methylate 1g and add wherein, the back that stirs adds glycol ether 10g, is warming up to 70～80 ℃, abundant stirring reaction 3～4h, the decompression precipitation adds TMPTA30g subsequently, continues to add behind 70～80 ℃ of abundant stirring reaction 4h in the tosic acid and free alkali, obtaining the M3 in the reaction formula, also is oligopolymer of the present invention (I).
The number-average molecular weight 2,000～3,000 of formula (I), viscosity 8,000～9,000 centipoise.
Embodiment 5: side chain contains the preparation of unsaturated functional group acrylate quasi-oligomer
In the 250mL there-necked flask of a band stirring and reflux exchanger, add 60g embodiment 1 or embodiment 2 resulting polymers M1, taking by weighing sodium methylate 1g adds wherein, add glycol ether 10g after stirring, be warming up to 70～80 ℃, fully stirring reaction 3～4h, the decompression precipitation, add MALEIC ANHYDRIDE 20g subsequently, temperature is controlled at 70～80 ℃, continues reaction 2h and obtains oligopolymer of the present invention (I).
The number-average molecular weight 2,500～3,000 of formula (I), viscosity 8,000～9,000 centipoise.
Embodiment 6: light solidifying paint composition
Take by weighing and add initiator 11730.5g stirring and evenly mixing again behind gained oligopolymer (I) 7.0g, TMPTA0.5g, EOEOEA0.5g, HDDA0.5g, BDDA0.5g, the PDDA0.5g mixing among the embodiment 3 and obtain Photocurable composition.
This Photocurable composition viscosity is 470s (N4), it is coated on the metal aluminum sheet, under UV or the irradiation of visible light source dysprosium lamp, promptly solidified in 5～10 seconds, paint film is transparent water-white, scratch hardness is greater than 2H, sticking power is 0 grade, and the 40cm shock resistance is passed through, and surveys water-fast, pure performance according to respective country standard GB/T1768-79 mensuration wear resisting property and GB/T9274-1988 infusion method and all meets national standard.
Embodiment 7: light solidifying paint composition
Take by weighing among the embodiment 3 and add initiator ITX0.5g again behind gained oligopolymer (I) 4.0g, epoxy acrylic resin 1.5g, polyurethane acrylic resin 1.5g, TMPTA0.5g, NPGDA1.0g, HDDA0.5g, the BDDA0.5g mixing, stirring and evenly mixing obtains Photocurable composition.
This Photocurable composition viscosity is 250s (N4), it is coated on the general steel plate, under UV or the irradiation of visible light source dysprosium lamp, promptly solidified in 5～10 seconds, paint film is faint yellow transparent, scratch hardness is greater than 2H, sticking power is 0 grade, and the 40cm shock resistance is passed through, and surveys water-fast, pure performance according to respective country standard GB/T1768-79 mensuration wear resisting property and GB/T9274-1988 infusion method and all meets national standard.
Embodiment 8: light solidifying paint composition
Take by weighing gained oligopolymer (I) 5.0g, epoxy acrylic resin 2.0g, PETA0.5g, EOEOEA0.5g, PO among the embodiment 3
3Add initiator 9070.5g stirring and evenly mixing behind-TMPTA0.5g, HDDA0.5g, the PDDA0.5g mixing again and obtain Photocurable composition.
This Photocurable composition viscosity is 220s (N4), it is coated on the stone material of Dali, under UV or the irradiation of visible light source dysprosium lamp, promptly solidified in 5～10 seconds, paint film is yellowish transparent, scratch hardness is greater than 2H, sticking power is 0 grade, surveys water-fast, pure performance according to respective country standard GB/T1768-79 mensuration wear resisting property and GB/T9274-1988 infusion method and all meets national standard.
Embodiment 9: light solidifying paint composition
Take by weighing gained oligopolymer (I) 5.0g among the embodiment 4, TMPTA1.0g, HDDA1.0g, TPGDA, PDDA0.5g, PEG (200) DA1.0g, ITX0.3g, EDB0.2g stirring and evenly mixing and obtain Photocurable composition.
This Photocurable composition viscosity is 150s (N4), it is coated on the aluminium, under UV or the irradiation of visible light source dysprosium lamp, promptly solidified in 5～10 seconds, paint film is yellowish transparent, scratch hardness is greater than 2H, sticking power is 0 grade, surveys water-fast, pure performance according to respective country standard GB/T1768-79 mensuration wear resisting property and GB/T9274-1988 infusion method and all meets national standard.
Embodiment 10: light solidifying paint composition
Take by weighing gained oligopolymer (I) 3.0g, epoxy acrylic resin 1.0g among the embodiment 5, vinylbenzene 2.0g, TMPTA1.0g, TPGDA1.0g, PDDA0.5g, PEG (200) DA1.0g, ITX0.3g, EDB0.2g stirring and evenly mixing and obtain Photocurable composition.
This Photocurable composition viscosity is 120s (N4), it is coated on the aluminium, under UV or the irradiation of visible light source dysprosium lamp, promptly solidified in 5～10 seconds, paint film is yellowish transparent, scratch hardness is greater than 2H, sticking power is 0 grade, surveys water-fast, pure performance according to respective country standard GB/T1768-79 mensuration wear resisting property and GB/T9274-1988 infusion method and all meets national standard.
Claims (10)
1. a side chain contains the acrylate quasi-oligomer of unsaturated functional group, and its structural formula is as shown in the formula (I):
Wherein,
A is-COOR
1, R wherein
1Be C
1～C
6Aliphatic alkyl or phenyl;
B is-COO (CH
2CH
2O)
nH ,-COO (CH
2)
nOH;
C is-COO (CH
2)
nOCOCH=CHCOOH,
-COO(CH
2CH
2O)
nCOCH＝CH
2COOH；
D is-COO (CH
2)
nOCOCH=CH
2,
-COO(CH
2)nOCOC(R)＝CH
2、
-COO(CH
2CH
2O)nCOCH＝CH
2、
-COO(CH
2CH
2O)
nCOC(R)＝CH
2，
Wherein, R is methyl or ethyl;
n
1, n
2, n
3And n
4Be respectively 1～150 integer independently;
n
1+n
2+n
3+n
4＝4～150；
N is 1～20 integer.
m
1It is 1～20 integer; m
2And m
3Be respectively 0～10 integer independently; m
2And m
3Can not be 0 simultaneously; m
1+ m
2+ m
3=3～60;
2. according to formula (I) oligopolymer of claim 1, wherein
A is-COOR
1, R wherein
1Be C
1～C
6Aliphatic alkyl or phenyl;
B is-COO (CH
2CH
2O)
nH ,-COO (CH
2)
nOH;
C is-COO (CH
2)
nOCOCH=CHCOOH,
-COO(CH
2CH
2O)
nCOCH＝CH
2COOH；
D is-COO (CH
2)
nOCOCH=CH
2,
-COO(CH
2)nOCOC(R)＝CH
2、
-COO(CH
2CH
2O)nCOCH＝CH
2、
-COO(CH
2CH
2O)
nCOC(R)＝CH
2，
Wherein, R is methyl or ethyl;
n
1, n
2, n
3And n
4Be respectively 1～150 integer independently;
n
1+n
2+n
3+n
4＝4～150；
N is 1～20 integer.
m
1It is 1～20 integer; m
2And m
3Be respectively 0～10 integer independently; m
2And m
3Can not be 0 simultaneously; m
1+ m
2+ m
3=3～60;
3. according to formula (I) oligopolymer of claim 1, wherein A is-COOR
1, R wherein
1Be C
1～C
4Aliphatic alkyl.
4. method for preparing following formula (I) oligopolymer,
Wherein,
A is-COOR
1, R wherein
1Be C
1～C
6Aliphatic alkyl or phenyl;
B is-COO (CH
2CH
2O)
nH ,-COO (CH
2)
nOH;
C is-COO (CH
2)
nOCOCH=CHCOOH,
-COO(CH
2CH
2O)
nCOCH＝CH
2COOH；
D is-COO (CH
2)
nOCOCH=CH
2,
-COO(CH
2)nOCOC(R)＝CH
2、
-COO(CH
2CH
2O)nCOCH＝CH
2、
-COO(CH
2CH
2O)
nCOC(R)＝CH
2，
Wherein, R is methyl or ethyl;
m
1It is 1～20 integer; m
2And m
3Be respectively 0～10 integer independently; m
2And m
3Can not be 0 simultaneously; m
1+ m
2+ m
3=3～60;
n
1, n
2, n
3And n
4Be respectively 1～150 integer independently;
n
1+n
2+n
3+n
4＝4～150；
N is 1～20 integer;
It is characterized in that described method comprises the steps:
Optional following steps the two one of or all,
Its condition is to work as m
2Or m
3Be 0 o'clock, described method does not comprise step 3 or step 4;
Wherein,
R
1Be C
1～C
6Fat alkane family's base or phenyl;
R
2Be HO (CH
2CH
2O)
nH, HO (CH
2)
nOH, n are 1～8 integers;
R
3It is Viscoat 295, acrylate, methacrylic ester, ethoxylation (3) Viscoat 295, pentaerythritol triacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, propoxylation (2) neopentylglycol diacrylate, 1, the 6-hexanediyl ester, PDDA, 1,4 butanediol diacrylate, propoxylation (3) glycerol tri-acrylate, the phthalic acid tripropylene glycol diacrylate, ethoxylation (4) bisphenol a diacrylate, dodecyl acrylate, the methacrylic dodecyl gallate, urethane acrylate, polyester acrylate;
R
4Be the C that contains two keys
4～C
5Dicarboxylic anhydride;
Cat
1Be initiator, chain-transfer agent and/or solvent;
Cat
2And Cat
3Can be identical or different, be Base or H
+, wherein, Base is low alkyl group sodium alkoxide, low alkyl group potassium alcoholate, sodium hydroxide, potassium hydroxide, sodium Metal 99.5; H
+Be Lewis acid or protonic acid.
5. according to the method for claim 4, wherein
R
1Be methyl, ethyl or propyl group;
R
2Be HO (CH
2CH
2O)
nH, HO (CH
2)
nOH, n are 1～4;
R
3Be to be selected from the following carboxylicesters that contains the two keys of C=C: acrylate, methacrylic ester, TMPTA, TPGDA, HDDA and BDDA;
R
4It is MALEIC ANHYDRIDE;
n
1, n
2, n
3And n
4Be respectively 10～30 independently; n
1+ n
2+ n
3+ n
4=20～40;
N is 20～40;
m
1Be 2～10; m
2And m
3Be respectively to be 1～5 independently; m
1+ m
2+ m
3=5～15;
Cat
1Can be initiator, chain-transfer agent and/or solvent, wherein initiator be Diisopropyl azodicarboxylate, dibenzoyl peroxide or dicumyl peroxide; Chain-transfer agent is thiomethyl alcohol, Virahol or lauryl mercaptan; Solvent is toluene, ethyl acetate, butylacetate or ethanol;
Cat
2And Cat
3Identical, be Base or H
+, wherein Base is sodium methylate, sodium ethylate or sodium Metal 99.5; H
+Be Lewis acid or protonic acid.
6. according to the method for claim 4 or 5, wherein, each step in the described method adopts following processing condition:
Step 1, polyacrylate(s) synthetic: with the acrylic ester monomer is raw material, adds Cat
1Initiator, solvent and chain-transfer agent, temperature of reaction are controlled at 35～120 ℃, and fully stirring reaction obtains product M1;
Step 2 is with M1 and R
2Reaction, M1 and R
2Material proportion is 1～8: 1, adds Base or H
+Catalyzer, its temperature of reaction are controlled at 45～150 ℃, and fully stirring reaction obtains product M2;
Optional following step the two one of or all,
Step 3 is with M2 and R
3Reaction, M2 and R
3Material proportion is 1～8: 1, adds Base or H
+Catalyzer, its stable reaction are controlled at 30～85 ℃, and fully stirring reaction obtains product M3;
Step 4 is with M2 or M3 and R
4Reaction, its temperature of reaction is controlled at 30～100 ℃, and fully stirring reaction obtains formula (I) oligopolymer.
7. according to the method for claim 6, wherein, each step in the described method adopts following processing condition:
Step 1, polyacrylate(s) synthetic: with the acrylic ester monomer is raw material, adds Cat
1Initiator, solvent and chain-transfer agent, temperature of reaction are controlled at 60～100 ℃, and fully stirring reaction obtains product M1;
Step 2 is with M1 and R
2Reaction, M1 and R
2Material proportion is 3～5: 1, adds Base or H
+Catalyzer, its temperature of reaction are controlled at 60～120 ℃, and fully stirring reaction obtains product M2;
Optional following step the two one of or all,
Step 3 is with M2 and R
3Reaction, M2 and R
3Material proportion is 3～5: 1, adds Base or H
+Catalyzer, its stable reaction are controlled at 50～90 ℃, and fully stirring reaction obtains product M3;
Step 4 is with M2 or M3 and R
4Reaction, its temperature of reaction is controlled at 50～90 ℃, and fully stirring reaction obtains formula (I) oligopolymer.
8. coating composition that contains arbitrary described formula (I) oligopolymer of claim 1-3, it contains formula (I) oligopolymer, light trigger, auxiliary agent and diluting monomer, wherein, formula (I) oligopolymer: light trigger: auxiliary agent: diluting monomer is 1.000: 0.010-0.100: 0.002-0.100: 0.100-10.000.
9. coating composition according to Claim 8, wherein, formula (I) oligopolymer: light trigger: auxiliary agent: the weight ratio of diluting monomer is 1.000: 0.020-0.050: 0.010-0.050: 0.500-3.000.
10. according to Claim 8 or 9 coating composition, wherein,
Light trigger is 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl-2-hydroxyl-1-phenyl-1-acetone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone or 2-isopropyl thioxanthone;
Auxiliary agent is defoamer, flow agent, mould inhibitor and/or dispersion moisture agent;
Diluting monomer is vinylbenzene, butyl acrylate, tripropylene glycol diacrylate, 1,3-butylene glycol diacrylate, Viscoat 295, pentaerythritol triacrylate, PDDA, 1,4 butanediol diacrylate or phthalic acid three propanedioic acid diacrylates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100691044A CN100486955C (en) | 2004-07-05 | 2004-07-05 | Acrylate kind oligomer with side chain containing unsaturated functional group, its proparation method and light solidifying paint composition containing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100691044A CN100486955C (en) | 2004-07-05 | 2004-07-05 | Acrylate kind oligomer with side chain containing unsaturated functional group, its proparation method and light solidifying paint composition containing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1718567A true CN1718567A (en) | 2006-01-11 |
| CN100486955C CN100486955C (en) | 2009-05-13 |
Family
ID=35930528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100691044A Expired - Fee Related CN100486955C (en) | 2004-07-05 | 2004-07-05 | Acrylate kind oligomer with side chain containing unsaturated functional group, its proparation method and light solidifying paint composition containing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100486955C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103589264A (en) * | 2013-10-25 | 2014-02-19 | 中国科学院广州化学研究所 | Ultraviolet light cured aqueous acrylate polymer coating and preparation method thereof |
| CN103627282A (en) * | 2013-10-25 | 2014-03-12 | 中国科学院广州化学研究所 | UV (Ultraviolet) photocurable acrylate polymer coating for BOPP (Biaxially-oriented Polypropylene) and preparation method thereof |
| CN103819994A (en) * | 2014-01-27 | 2014-05-28 | 中科院广州化学有限公司 | UV (ultraviolet)-curable acrylate polymer water emulsion for coating polypropylene film |
| CN103865351A (en) * | 2014-02-21 | 2014-06-18 | 中科院广州化学有限公司 | UV (Ultraviolet) photocuring polyacrylate-chlorinated polypropylene compound aqueous emulsion for BOPP (Biaxially-oriented Polypropylene) coating and preparation method and application thereof |
| CN105916899A (en) * | 2013-11-21 | 2016-08-31 | 3M创新有限公司 | Liquid optical adhesive compositions |
| CN109294511A (en) * | 2018-09-03 | 2019-02-01 | 佛山艾仕仑科技有限公司 | A kind of UV curing adhesive suitable for flexible parent metal bonding |
| CN110903799A (en) * | 2019-12-02 | 2020-03-24 | 武汉市科达云石护理材料有限公司 | Water-based light-cured stone decorative surface adhesive |
| CN115197381A (en) * | 2022-09-16 | 2022-10-18 | 广州鹿山新材料股份有限公司 | Unsaturated SMA resin modified polypropylene and preparation method thereof |
-
2004
- 2004-07-05 CN CNB2004100691044A patent/CN100486955C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103627282A (en) * | 2013-10-25 | 2014-03-12 | 中国科学院广州化学研究所 | UV (Ultraviolet) photocurable acrylate polymer coating for BOPP (Biaxially-oriented Polypropylene) and preparation method thereof |
| CN103589264A (en) * | 2013-10-25 | 2014-02-19 | 中国科学院广州化学研究所 | Ultraviolet light cured aqueous acrylate polymer coating and preparation method thereof |
| CN103589264B (en) * | 2013-10-25 | 2015-11-18 | 中国科学院广州化学研究所 | A kind of UV-curable water-borne acrylic ester polymer coating and preparation method thereof |
| CN103627282B (en) * | 2013-10-25 | 2016-01-20 | 中国科学院广州化学研究所 | BOPP UV light-cured acrylate polymer coating and preparation method thereof |
| CN105916899B (en) * | 2013-11-21 | 2019-01-18 | 3M创新有限公司 | Optics of liquids adhesive composition |
| CN105916899A (en) * | 2013-11-21 | 2016-08-31 | 3M创新有限公司 | Liquid optical adhesive compositions |
| CN103819994A (en) * | 2014-01-27 | 2014-05-28 | 中科院广州化学有限公司 | UV (ultraviolet)-curable acrylate polymer water emulsion for coating polypropylene film |
| CN103819994B (en) * | 2014-01-27 | 2016-01-20 | 中科院广州化学有限公司 | A kind of polypropylene film coating UV light-cured acrylate aqueous polymer dispersion |
| CN103865351A (en) * | 2014-02-21 | 2014-06-18 | 中科院广州化学有限公司 | UV (Ultraviolet) photocuring polyacrylate-chlorinated polypropylene compound aqueous emulsion for BOPP (Biaxially-oriented Polypropylene) coating and preparation method and application thereof |
| CN109294511A (en) * | 2018-09-03 | 2019-02-01 | 佛山艾仕仑科技有限公司 | A kind of UV curing adhesive suitable for flexible parent metal bonding |
| CN109294511B (en) * | 2018-09-03 | 2021-06-01 | 佛山艾仕仑科技有限公司 | UV curing adhesive suitable for bonding flexible base materials |
| CN110903799A (en) * | 2019-12-02 | 2020-03-24 | 武汉市科达云石护理材料有限公司 | Water-based light-cured stone decorative surface adhesive |
| CN110903799B (en) * | 2019-12-02 | 2021-08-17 | 武汉市科达云石护理材料有限公司 | Water-based light-cured stone decorative surface adhesive |
| CN115197381A (en) * | 2022-09-16 | 2022-10-18 | 广州鹿山新材料股份有限公司 | Unsaturated SMA resin modified polypropylene and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100486955C (en) | 2009-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101747594B (en) | Epoxy acrylate prepolymer resin and preparation method thereof and application in photocurable coating | |
| CN100343344C (en) | Ultraviolet curing coating for metal plating surface protection | |
| CN1746235A (en) | Ultraviolet aluminium-silver size coating with light curing | |
| CN102086372B (en) | Radiation curing adhesive and preparation method thereof | |
| CN101928541B (en) | UV curable adhesive | |
| CN101709196B (en) | Light mixing cured coating composition and preparation method thereof | |
| CN100999643A (en) | Crystal whisker wear-resistant ultraviolet ray solidified paint and preparation process thereof | |
| CN108384406B (en) | Graphene oxide UV (ultraviolet) curing coating and preparation method thereof | |
| CN1134480C (en) | Unsaturated polyester resin and the use of it | |
| CN106010144A (en) | UV-LED-curing optical fiber coating resin and preparing method and application thereof | |
| CN1959530A (en) | Ultraviolet light solidified coating in use for post processing of imaging material | |
| CN1185309C (en) | UV curable compositions for producing mar resistant coatings and method for depositing same | |
| CN110467704A (en) | A kind of 3D printing LED light solidification flexible photosensitive resin and preparation method thereof | |
| CN104017496A (en) | Ultraviolet light polymerized low polymer synthesized by utilizing rosin derivatives and preparation method of polymer | |
| CN1718567A (en) | Acrylate kind oligomer with side chain containing unsaturated functional group, its proparation method and light solidifying paint composition containing same | |
| CN109135413A (en) | A kind of mute sand oil ink of LED-UV offset printing and preparation method thereof | |
| CN110229317A (en) | UV curable unsaturated polyester resin of high-vinyl degree of functionality and the preparation method and application thereof | |
| CN1010292B (en) | Sheet molding compound (SMC) and surface layer thereof | |
| CN1297972A (en) | Ultravoilet cured paint without irritation | |
| CN1297973A (en) | Ultraviolet cured paint | |
| CN1422288A (en) | Composition | |
| CN1297974A (en) | Ultraviolet cured paint without yellowing | |
| CN1177365A (en) | Reaction curable composition and solid surface material | |
| CN101074277A (en) | Esterified acrylie-ester high-polymer, its synthesis and use | |
| CN1239547C (en) | Curable unsaturated resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: BEIJING ZIGUANG YING LI CHEMICAL TECHNOLOGY CO., L Free format text: FORMER NAME: QINGHUAZIGUANG YINGLI CHEMICAL TECHNOLOGY CO. LTD., BEIJING |
|
| CP03 | Change of name, title or address |
Address after: No. 18 Anning East Road, Beijing, Haidian District Patentee after: TH-UNIS Insight Co., Ltd. Address before: No. 18 Anning East Road, Beijing, Haidian District Patentee before: Beijing Tsinghua Unisplendour Insight Chemical Technology LLC |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090513 Termination date: 20130705 |