CN101845129B - Silicone (methyl)acrylate ABA-type block copolymer, and preparation method and application thereof - Google Patents
Silicone (methyl)acrylate ABA-type block copolymer, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a silicone (methyl)acrylate ABA-type block copolymer, and a production method and application thereof in the preparation of a composite coating. The copolymer has a structure shown in a formula I. The composite coating is prepared by stirring for 1 to 3 hours in a constant-temperature high-speed disperser the following components in part by mass: 1 to 100 parts of silicone (methyl)acrylate ABA-type block copolymer, 0 to 100 parts of (methyl)acrylate polymer, 0.2 to 5 parts of defoamer, 0.2 to 4 parts of dispersing agent, 40 to 100 parts of inorganic salt filler and 50 to 100 parts of solvent. As the two ends of the ABA-type block copolymer are still (methyl)acrylate, a silicone component is added without influencing the adhesive capacity, the smudge resistance and stability of the coating are improved, and the coating has the relatively higher comprehensive performance of water resistance, the smudge resistance, heat resistance, age resistance and the like.
Description
Technical field
The invention belongs to the chemistry painting industry technical field, particularly a kind of organosilicon (methyl) propenoate ABA block polymer and preparation method thereof and the application in the preparation composite coating.
Background technology
With (methyl) propenoate is that the acrylate paint that main raw material is processed is one type of important coating variety, has excellent UV resistance, resistance to acids and bases and oxidation-resistance, and because of containing the polarity ester group in the molecule, its oil-proofness and chemical resistance are also preferable.But because its constructional feature, (methyl) acrylate paint its water tolerance when having better adhesive power is relatively poor, and simultaneously, (methyl) acrylic ester polymer particularly easy high temperature of simple linear polymer is clamminess, and contamination resistance descends, and low temperature becomes fragile, the toughness variation.
In order to improve the over-all properties of (methyl) acrylate paint, usually to carry out modification to it.ZGK 5 is one type of application elemento-organic polymer very widely, because structure, it has good hydrophobic nature; Simultaneously, the Si-O covalent bond energy is 425 kj/mol, and is bigger than common C-C bond energy (345 kj/mol); This makes organosilicon material have good thermotolerance, resistant of high or low temperature, water tolerance, chemical proofing and unsurpassed weather resistance; But on the other hand, the adhesive power of organosilicon material and base material is relatively poor, therefore utilizes organic-silicon-modified (methyl) acrylate paint; Be expected the comprehensively advantage of the two, improve the over-all properties of coating greatly.
Organic-silicon-modified (methyl) propenoate method commonly used, as: with double bond containing siloxanes (or silane coupling agent), particularly double bond containing siloxane oligomer is free-radical polymerized with (methyl) acrylic ester monomer; With an organosilane monomer and acrylate monomer compound nuclear/shell letex polymerization stage by stage under certain condition; Or the like.
Aforesaid method does not reach modified effect at organosilicon content after a little while, when organosilicon reaches certain content, again can be crosslinked, and poor stability, and also preparation often is random copolymers, can reduce the ADHESION OF PAINTS ability when organosilicon content is higher.
Summary of the invention
In order to solve the weak point that exists in the above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of organosilicon (methyl) propenoate ABA block polymer.
Another object of the present invention is to provide the preparation method of above-mentioned organosilicon (methyl) propenoate ABA block polymer.
Another purpose of the present invention is to provide a kind of organic silicon acrylic ester composite coating that is prepared from above-mentioned organosilicon (methyl) propenoate ABA block polymer; This coating cost is low, and adhesive ability is good, and is water-fast, and washability is heat-resisting, and is ageing-resistant.
A purpose more of the present invention is to provide the preparation method of above-mentioned composite coating; This method is by ATRP synthetic organosilicon (methyl) propenoate ABA block polymer, (methyl) acrylic ester polymer and color stuffing etc., stirs in the normal temperature high speed dispersor, is mixed with the method for coating.
The object of the invention is realized through following technical proposals: a kind of organosilicon (methyl) propenoate ABA block polymer, and said multipolymer has suc as formula the structure shown in 1:
Formula 1
m
1Or m
2It is 2～200 natural number;
N is 2～50 natural number;
R is that ester group is or/and the alkyl of carbonatoms 1～8;
R
1Be H or CH
3
R
2For carbon chain lengths is C
1～C
20Alkyl;
X is Cl atom or Br atom.
The preparation method of above-mentioned organosilicon (methyl) propenoate ABA block polymer; Comprise following operation steps: 100 mass parts (methyl) acrylate monomer, the end capped ZGK 5 of 1～300 mass parts bromine or the end capped dimethyl-of chlorine (siloxanes and ZGK 5), 0.1～50 mass parts coordination agent and 1～500 mass parts organic solvent are mixed; Cryosel is bathed freezing; Vacuumize, drum nitrogen 3～5 times is with deoxygenation; Under nitrogen protection, be warming up to 30～150 ℃ then, add 0.1～50 mass parts of catalyst reaction, 1.5～25h, obtain organosilicon (methyl) propenoate ABA block polymer.
Said (methyl) acrylate monomer is universal (methyl) propenoate, is preferably in (methyl) methyl acrylate and (methyl) NSC 20949 more than one;
The end capped ZGK 5 of said bromine prepares as follows: 100 mass parts end-vinyl ZGK 5,50 mass parts acetone, 200 mass parts hydrogen bromide-acetums are mixed; 50 ℃ are stirred 5h down; With zero(ppm) water extraction 5 times; Use Rotary Evaporators at 90 ℃ of rotary evaporation 4h again, obtain the end capped ZGK 5 of bromine;
Said coordination agent is the straight-chain paraffin or the triphenylphosphine of dipyridyl and verivate thereof, many nitrogen;
Said organic solvent is a toluene, 1,4-dioxane or butanone.
Said catalyzer is the lower valency metal halide.
Hydrogen bromide quality percentage composition >=40% of said hydrogen bromide acetic acid solution; Said dipyridyl and verivate thereof are preferably 2, the 2-dipyridyl; The straight-chain paraffin of said many nitrogen is preferably pentamethyl-diethylenetriamine (PMDETA); Said lower valency metal halide is preferably cuprous bromide or ferrous bromide.
A kind of composite coating that is prepared from above-mentioned organosilicon (methyl) propenoate ABA block polymer, said composite coating is formed by following feedstock production according to the mass fraction:
1～100 part of organosilicon (methyl) propenoate ABA block polymer
0～100 part of (methyl) acrylic ester polymer
50～100 parts of organic solvents
40～100 parts of inorganic salt fillers
0.2～5 part of skimmer
0.2～4 part of dispersion agent.
Said inorganic salt filler is white titanium pigment, talcum powder, light calcium carbonate or water-ground limestone; Said skimmer is mineral oil defoaming agent or ZGK 5 defoamer; Said dispersion agent is acrylate, polyacrylate or carboxylic acid sodium salt; Said solvent is a toluene, 1,4-dioxane or butanone.
The preparation method of said (methyl) acrylic ester polymer is by following operation steps: will (methyl) acrylate monomer 20～40 mass parts, initiator 1～4 mass parts and the mixing of organic solvent 40～60 mass parts, under the vacuum condition in 70～80 ℃ of temperature stirring reaction 12～16h.
Said (methyl) acrylate monomer is universal (methyl) propenoate, more than one in preferred (methyl) methyl acrylate and (methyl) NSC 20949; Said initiator is 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 4,4 '-azo (4-cyanopentanoic acid), tert-butyl peroxy acetate or peroxidized t-butyl perbenzoate; Said solvent is a toluene, 1,4-dioxane or butanone.
The preparation method of above-mentioned composite coating; Comprise following operation steps: after organosilicon (methyl) propenoate ABA block polymer, (methyl) acrylic ester polymer, organic solvent, inorganic salt filler, skimmer and dispersant; In the normal temperature high speed dispersor, stir 1～3h, obtain composite coating.
The present invention has following advantage and beneficial effect with respect to prior art:
Composite coating of the present invention is formulated by ATRP (ATRP) synthetic ABA type organosilicon (methyl) acrylate block copolymer, (methyl) acrylic ester polymer and color stuffing etc.; Compare with traditional organosilicon (methyl) acrylate paint; Because the ABA block polymer two ends still are (methyl) propenoate; So when not influencing adhesive ability, added the organosilicon composition; Improved the over-all properties of coating; And organosilicon and (methyl) propenoate be prepared in same the molecular chain, having improved the stability of this coating greatly, gained coating has performances such as water tolerance, contamination resistance, abrasion resistance, thermotolerance and stability to aging preferably.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
Test is all by following standard among all embodiment:
Film adhesive: press GB/T 1720-1979 (1989) and measure
Hardness of film: press GB/T 6739-1996 (determination of pencil hardness method) and measure
The abrasion resistance of filming: press GB/T9266-1998 and measure
Be coated with temper(ing) property: press GB/T1865-88 and measure
With water contact angle: adopt contact angle measurement to measure the contact angle of zero(ppm) water on film coated surface, all are measured all and measure down at 25 ℃.
Embodiment 1
Table 1: composite coating of the present invention and performance (I)
| Prescription | Organosilicon methacrylic ester ABA block polymer: acrylic ester polymer: other components (mass ratio) | Sticking power/level | With water contact angle/° | Pencil hardness | Abrasion resistance | Artificial ageing resistance/600h |
| 1 | 0∶100∶102 | 1 | 70 | H | ≤1500 | Foaming comes off |
| 2 | 15∶85∶102 | 1 | 90 | H | ≥2000 | Non-foamingly do not come off |
| 3 | 30∶70∶102 | 1 | 92 | H | ≥2500 | Non-foamingly do not come off |
| 4 | 50∶50∶102 | 1 | 97 | H | ≥2700 | Non-foamingly do not come off |
| 5 | 70∶30∶102 | 1 | 101 | H | ≥3000 | Non-foamingly do not come off |
In table 1; The preparation method of organosilicon methacrylic ester ABA block polymer is: with TEB 3K, 0.1 mass parts 2 of the end capped ZGK 5 of 20 mass parts bromines (Mn=1800), 80 mass parts; 2 '-dipyridyl and 100 mass parts butanone mix; It is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3 times is with deoxygenation; Under nitrogen protection, be warming up to 30 ℃ then, add 0.1 mass parts cuprous bromide reaction 25h, obtain organosilicon methacrylic ester ABA block polymer.The end capped ZGK 5 of bromine is processed according to following method: 100 mass parts end-vinyl ZGK 5 (Mn=1800), 50 mass parts acetone, hydrogen bromide acetic acid solution (the quality percentage composition of hydrogen bromide is 40%) that 200 mass parts are saturated are mixed; Stir 5h in 50 ℃; Product is through zero(ppm) water extraction 5 times, and 90 ℃ of rotary evaporation 4h of Rotary Evaporators make.
The preparation method of methacrylate polymers: 15 parts of TEB 3Ks, 25 parts of Octyl methacrylates, 30 parts of NSC 20949s, 30 parts of vinylformic acid heptyl esters; 2; 30 parts of 2 '-Diisopropyl azodicarboxylates and 500 parts of mixing of butanone, vacuum, stirring are reacted 13h down in 75 ℃.
Other components are 0.2 part of organic silicone oil, 1.8 parts of sodium acrylates, 100 parts of white titanium pigment fillers.
By proportioning in the table the above-mentioned organosilicon that makes (methyl) propenoate ABA block polymer, methacrylate polymers and other components are mixed, stir 3h in the normal temperature high speed dispersor and get composite coating.
The performance of the composite coating of the present invention that provides from table 1: 1. fill a prescription and 2～5 compare with prescription 1; Owing to added organosilicon methacrylic ester ABA block polymer; The hydrophobic nature of coating, abrasion resistance, stability to aging are improved greatly, and sticking power and hardness do not descend; 2. fill a prescription in 2～5 along with the increase of organosilicon content, the hydrophobic nature of coating, abrasion resistance, stability to aging increase.Table 1 data have demonstrated fully technique effect of the present invention.
Embodiment 2
Table 2 composite coating of the present invention and performance (II)
| Prescription | The methacrylic ester kind of preparation segmented copolymer | Sticking power/level | With water contact angle/° | Pencil hardness | Abrasion resistance | Artificial ageing resistance/600h |
| Segmented copolymer 1 | TEB 3K | 1 | 90 | H | ≥2500 | Non-foamingly do not come off |
| Segmented copolymer 2 | N-BMA, TEB 3K | 1 | 94 | H | ≥2500 | Non-foamingly do not come off |
| Segmented copolymer 3 | Propenoic acid, 2-methyl, isobutyl ester, Octyl methacrylate, methyl acrylate | 1 | 95 | H | ≥2500 | Non-foamingly do not come off |
| Segmented copolymer 4 | Octyl acrylate, methacrylic heptyl heptylate | 1 | 120 | H | ≥2500 | Non-foamingly do not come off |
In table 2; The preparation method of organosilicon methacrylic ester ABA block polymer is: the end capped ZGK 5 of 30 mass parts bromines (Mn=3000); The methacrylic ester (wherein the methacrylic ester of segmented copolymer 2～4 proportioning be 7: 3,4: 4: 2 and 6: 4) in order shown in table of 70 mass parts, and 0.5 mass parts 2,2 '-dipyridyl and 100 mass parts toluene mix; It is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3 times is with deoxygenation; Under nitrogen protection, be warming up to 70 ℃ then, add 0.6 mass parts cuprous bromide reaction 15h, obtain organosilicon methacrylic ester ABA block polymer.The end capped ZGK 5 of bromine is processed according to following method: 100 mass parts end-vinyl ZGK 5 (Mn=3000), 50 mass parts acetone, hydrogen bromide acetic acid solution (the quality percentage composition of hydrogen bromide is 40%) that 200 mass parts are saturated are mixed; Stir 5h in 50 ℃; Product is through zero(ppm) water extraction 5 times, and 90 ℃ of rotary evaporation 4h of Rotary Evaporators make.
The preparation method of methacrylate polymers: 30 parts of methyl acrylates, 20 parts of Octyl methacrylates, 35 parts of Propenoic acid, 2-methyl, isobutyl esters, 15 parts of vinylformic acid heptyl esters; 2; 2 parts of 2 '-Diisopropyl azodicarboxylates and 40 parts of mixing of butanone, vacuum, stirring are reacted 10h down in 75 ℃.
Other components are 0.2 part of organic silicone oil, 1.8 parts of sodium acrylates, 100 parts of white titanium pigment fillers.
By proportioning in the table above-mentioned organosilicon methacrylic ester ABA block polymer 20 mass parts, methacrylate polymers 80 mass parts and other components that makes mixed, stir 2h in the normal temperature high speed dispersor and get composite coating.
The performance of composite coating of the present invention is provided from table 2 prescription 1～4; During identical organosilicon content; Change the structure (homopolymer or multipolymer) of ABA block polymer A section; Performances such as ADHESION OF PAINTS ability, hydrophobic nature, hardness, abrasion resistance, stability to aging have analog result, demonstrate fully technique effect of the present invention.
Embodiment 3
(1) the end capped ZGK 5 of bromine is processed according to following method: 100 mass parts end-vinyl ZGK 5 (Mn=400), 50 mass parts acetone, hydrogen bromide-acetum that 200 mass parts are saturated are mixed; Stir 5h in 50 ℃; Product is through zero(ppm) water extraction 5 times, 90 ℃ of rotary evaporation 4h of Rotary Evaporators.
(2) preparation of organic silicon acrylic ester ABA block polymer: in the there-necked flask of 100mL, add 100 mass parts methyl acrylates, the end capped ZGK 5 of 1 mass parts bromine (Mn=400), 0.1 mass parts 2; 2 '-dipyridyl and 500 mass parts butanone mix; It is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3 times is with deoxygenation; Then under nitrogen protection; Be warming up to 30 ℃; Add 0.1 mass parts cuprous bromide reaction 25h, the organic silicon acrylic ester ABA block polymer, confirm that according to experimental principle and ir spectra, NMR spectrum, GPC data this organic silicon acrylic ester ABA block polymer structure is suc as formula shown in 2; M=200, n=2.
(formula 2)
(3) preparation of composite coating: get above-mentioned organic silicon acrylic ester ABA block polymer 100 mass parts; 0.2 part of organic silicone oil, 2 parts of sodium acrylates mix, and add 80 parts white titanium pigment filler again; 50 parts butanone stirs 1h and gets composite coating in the normal temperature high speed dispersor.The back survey performance of filming is following: 1 grade of sticking power, and with 99 ° of water contact angles, pencil hardness H, abrasion resistance >=2500, artificial ageing resistance/600h is non-foaming not to come off.
Embodiment 4
(1) the end capped ZGK 5 of bromine is processed according to following method: with embodiment 3 steps (1); Difference only is handled ZGK 5 (Mn=4700).
(2) preparation of organosilicon methacrylic ester ABA block polymer: in the there-necked flask of 100mL, add 100 mass parts methylacrylic acid eicosyl esters, the end capped ZGK 5 of 300 mass parts bromines (Mn=4700), 50 mass parts pentamethyl-diethylenetriamines and 1 mass parts 1; The 4-dioxane mixes; It is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3 times is with deoxygenation; Under nitrogen protection, be warming up to 150 ℃ then, add 50 mass parts cuprous bromides reaction 1.5h, obtain organosilicon methacrylic ester ABA block polymer.Confirm this organosilicon methacrylic ester ABA block polymer structure suc as formula shown in 3, m=2, n=50 according to experimental principle and ir spectra, NMR spectrum, GPC data.
(formula 3)
(3) preparation of composite coating: get above-mentioned organosilicon methacrylic ester ABA block polymer 70 mass parts; The powerful stirring down adds 5 parts of organic silicone oils, 0.2 part of carboxylic acid sodium, mixes, and adds 40 parts talcum powder again; 100 parts toluene, the powerful 3h that stirs gets composite coating.The back survey performance of filming is following: 1 grade of sticking power, and with 100 ° of water contact angles, pencil hardness H, abrasion resistance >=2500, artificial ageing resistance/600h is non-foaming not to come off.
Embodiment 5
(1) the end capped ZGK 5 of bromine is processed according to following method: with embodiment 3 steps (1); Difference only is handled ZGK 5 (Mn=3800).
(2) preparation of organosilicon methacrylic ester ABA block polymer: in the there-necked flask of 100mL, add 1 mass parts n-BMA, the end capped ZGK 5 of 20 mass parts bromines (Mn=3800), 0.1 mass parts triphenylphosphine and 500 mass parts toluene and mix; It is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3 times is with deoxygenation; Then under nitrogen protection; Be warming up to 80 ℃; Add 50 mass parts ferrous bromides reactions 3h, obtain organosilicon methacrylic ester ABA block polymer, confirm that according to experimental principle and ir spectra, NMR spectrum, GPC data this organosilicon methacrylic ester ABA block polymer structure is suc as formula shown in 4; M=65, n=40.
(formula 4)
(3) preparation of composite coating: get above-mentioned organosilicon methacrylic ester ABA block polymer 70 mass parts; The powerful stirring adds 0.2 part of organic silicone oil, 4 parts of ZX-Is down; Mix; The light calcium carbonate filler that adds 100 parts again, 100 parts toluene, the powerful 3h that stirs gets composite coating.The back survey performance of filming is following: 1 grade of sticking power, and with 105 ° of water contact angles, pencil hardness H, abrasion resistance >=2500, artificial ageing resistance/600h is non-foaming not to come off.
Embodiment 6
(1) preparation of organic silicon acrylic ester ABA block polymer: in the there-necked flask of 100mL, add 40 mass parts methyl acrylates, 60 mass parts n-butyl acrylates, the end capped dimethyl-of 10 mass parts chlorine (siloxanes and ZGK 5) (Mn=3000), 40 mass parts triphenylphosphines and 1 mass parts toluene mixes; It is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3 times is with deoxygenation; Then under nitrogen protection; Be warming up to 80 ℃, add 0.1 mass parts ferrous bromide reaction 3h, obtain the organic silicon acrylic ester ABA block polymer; Confirm that according to experimental principle and ir spectra, NMR spectrum, GPC data this organic silicon acrylic ester ABA block polymer structure is suc as formula shown in 5; M=157, n=39, R are CH
3Or C
4H
9
(formula 5)
(2) preparation of composite coating: get above-mentioned organic silicon acrylic ester ABA block polymer 70 mass parts; The powerful stirring down adds 5 parts of organic silicone oils, 3 parts of sodium acrylates, mixes, and adds 40 parts heavy calcium carbonate filling again; 50 parts toluene, the powerful 2h that stirs gets composite coating.The back survey performance of filming is following: 1 grade of sticking power, and with 103 ° of water contact angles, pencil hardness H, abrasion resistance >=2500, artificial ageing resistance/600h is non-foaming not to come off.
Embodiment 7
(1) the end capped ZGK 5 of bromine is processed according to following method: with embodiment 3 steps (1); Difference only is handled ZGK 5 (Mn=4300).
(formula 6)
(2) preparation of organosilicon methacrylic ester ABA block polymer: in the there-necked flask of 100mL, add 100 mass parts n octyl methacrylates, the end capped ZGK 5 of 150 mass parts bromines (Mn=4300), 30 mass parts pentamethyl-diethylenetriamines and 200 mass parts butanone and mix; It is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3 times is with deoxygenation; Then under nitrogen protection; Be warming up to 100 ℃; Add 0.5 mass parts cuprous bromide reaction 2.5h, obtain organosilicon methacrylic ester ABA block polymer, confirm that according to experimental principle and ir spectra, NMR spectrum, GPC data this organosilicon (methyl) propenoate ABA block polymer structure is suc as formula shown in 6; M=7, n=45.
(3) preparation of composite coating: get 1 part of above-mentioned organosilicon methacrylic ester ABA block polymer, the powerful stirring down adds 3 parts of organic silicone oils, 2 parts of carboxylic acid sodium, mixes; The white titanium pigment filler that adds 80 parts again; 100 parts 1, the 4-dioxane, the powerful 2h that stirs gets composite coating.The back survey performance of filming is following: 1 grade of sticking power, and with 110 ° of water contact angles, pencil hardness H, abrasion resistance >=2500, artificial ageing resistance/600h is non-foaming not to come off.
Embodiment 8
(1) the end capped ZGK 5 of bromine is processed according to following method: with embodiment 3 steps (1); Difference only is handled ZGK 5 (Mn=2000).
(2) preparation of organic silicon acrylic ester ABA block polymer: in the there-necked flask of 100mL, add 100 mass parts Bing Xisuandingzhis, the end capped ZGK 5 of 10 mass parts bromines (Mn=2000), 0.1 mass parts pentamethyl-diethylenetriamine and 100 mass parts butanone and mix; It is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3 times is with deoxygenation; Then under nitrogen protection; Be warming up to 100 ℃; Add 0.8 mass parts cuprous bromide reaction 2.5h, obtain the organic silicon acrylic ester ABA block polymer, confirm that according to experimental principle and ir spectra, NMR spectrum, GPC data this organic silicon acrylic ester ABA block polymer structure is suc as formula shown in 7; M=75, n=20.
(formula 7)
(3) preparation of composite coating: get 1 part of above-mentioned organic silicon acrylic ester ABA block polymer, the powerful stirring down adds 3 parts of organic silicone oils, 2 parts of carboxylic acid sodium, mixes; The white titanium pigment filler that adds 80 parts again; 100 parts 1, the 4-dioxane, the powerful 2h that stirs gets composite coating.The back survey performance of filming is following: 1 grade of sticking power, and with 110 ° of water contact angles, pencil hardness H, abrasion resistance >=2500, artificial ageing resistance/600h is non-foaming not to come off.
Embodiment 9
(1) the end capped ZGK 5 of bromine is processed according to following method: with embodiment 3 steps (1); Difference only is handled ZGK 5 (Mn=1600).
(2) preparation of organic silicon acrylic ester ABA block polymer: in the there-necked flask of 100mL, add 100 mass parts Bing Xisuandingzhis, the end capped ZGK 5 of 12 mass parts bromines (Mn=1600), 0.2 mass parts pentamethyl-diethylenetriamine and 100 mass parts butanone and mix; It is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3 times is with deoxygenation; Then under the nitrogen protection; Be warming up to 100 ℃; Add 0.8 mass parts cuprous bromide reaction 2.5h, obtain the organic silicon acrylic ester ABA block polymer, confirm that according to experimental principle and ir spectra, NMR spectrum, GPC data this organic silicon acrylic ester ABA block polymer structure is suc as formula shown in 8; M=80, n=15.
(formula 8)
(3) preparation of methacrylate polymers: in the there-necked flask of 100mL, add 20 mass parts TEB 3Ks, 25 mass parts Propenoic acid, 2-methyl, isobutyl esters, 35 mass parts Octyl acrylates, 20 mass parts methylacrylic acid eicosyl ester monomers; 2; 2 '-azo two (2; The 4-methyl pentane nitrile) 4 parts and 40 parts of mixing of toluene, 12h is reacted in vacuum, stirring down in 70 ℃, get methacrylate polymers.
(4) preparation of composite coating: get above-mentioned organic silicon acrylic ester ABA block polymer 1 mass parts; 100 parts of methacrylate polymers, the powerful stirring down adds 2 parts of organic silicone oils, 2 parts of ZX-Is, mixes; The white titanium pigment filler that adds 80 parts again; 70 parts 1, the 4-dioxane, the powerful 3h that stirs gets composite coating.The back survey performance of filming is following: 1 grade of sticking power, and with 104 ° of water contact angles, pencil hardness H, abrasion resistance >=2500, artificial ageing resistance/600h is non-foaming not to come off.
Embodiment 10
(1) the end capped ZGK 5 of bromine is processed according to following method: with embodiment 3 steps (1); Difference only is handled ZGK 5 (Mn=4000)
(2) adding 100 mass parts Octyl acrylates, the end capped ZGK 5 of 25 mass parts bromines (Mn=4000), 0.3 mass parts pentamethyl-diethylenetriamine and 100 mass parts toluene in the there-necked flask that is prepared in 100mL of organic silicon acrylic ester ABA block polymer mixes; It is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3 times is with deoxygenation; Then under the nitrogen protection; Be warming up to 105 ℃; Add 0.7 mass parts cuprous bromide reaction 3h, obtain the organic silicon acrylic ester ABA block polymer, confirm that according to experimental principle and ir spectra, NMR spectrum, GPC data this organic silicon acrylic ester ABA block polymer structure is suc as formula shown in 9; M=10, n=40.
(formula 9)
(3) preparation of acrylic ester polymer: in the there-necked flask of 100mL, add 30 mass parts methyl acrylates, 25 mass parts Octyl acrylates, 35 mass parts Bing Xisuandingzhis, 10 mass parts methylacrylic acid pentyl ester monomer monomers; 1 part of peroxidized t-butyl perbenzoate and 60 parts of mixing of toluene; 16h is reacted in vacuum, stirring down in 80 ℃, get acrylic ester polymer.
(4) preparation of composite coating: get above-mentioned organic silicon acrylic ester ABA block polymer 100 mass parts; 100 parts of acrylic ester polymers, the powerful stirring down adds 1 part of organic silicone oil, 1 part of ZX-I, mixes; The white titanium pigment filler that adds 85 parts again; 75 parts 1, the 4-dioxane, the powerful 2h that stirs gets composite coating.The back survey performance of filming is following: 1 grade of sticking power, and with 104 ° of water contact angles, pencil hardness H, abrasion resistance >=2500, artificial ageing resistance/600h is non-foaming not to come off.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. an organosilicon (methyl) propenoate ABA block polymer, it is characterized in that: said multipolymer has suc as formula the structure shown in 1:
m
1Or m
2It is 2～200 natural number;
N is 2～50 natural number;
R is that ester group is or/and the alkyl of carbonatoms 1～8;
R
1Be H or CH
3
R
2For carbon chain lengths is C
1～C
20Alkyl;
X is Cl atom or Br atom.
2. the preparation method of a kind of organosilicon according to claim 1 (methyl) propenoate ABA block polymer; It is characterized in that comprising following operation steps: 100 mass parts (methyl) acrylate monomer, the end capped ZGK 5 of 1～300 mass parts bromine, 0.1～50 mass parts coordination agent and 1～500 mass parts organic solvent are mixed; Cryosel is bathed freezing; Vacuumize, drum nitrogen 3～5 times is with deoxygenation; Under nitrogen protection, be warming up to 30～150 ℃ then, add 0.1～50 mass parts of catalyst reaction, 1.5～25h, obtain organosilicon (methyl) propenoate ABA block polymer.
3. preparation method according to claim 2 is characterized in that:
Said (methyl) acrylate monomer is universal (methyl) propenoate;
The end capped ZGK 5 of said bromine prepares as follows: 100 mass parts end-vinyl ZGK 5,50 mass parts acetone, 200 mass parts hydrogen bromide acetic acid solutions are mixed; 50 ℃ are stirred 5h down; With zero(ppm) water extraction 5 times; Use Rotary Evaporators at 90 ℃ of rotary evaporation 4h again, obtain the end capped ZGK 5 of bromine;
Said coordination agent is the straight-chain paraffin or the triphenylphosphine of dipyridyl and verivate thereof, many nitrogen;
Said organic solvent is a toluene, 1,4-dioxane or butanone;
Said catalyzer is the lower valency metal halide.
4. preparation method according to claim 3 is characterized in that: said universal (methyl) propenoate is more than one in (methyl) methyl acrylate and (methyl) NSC 20949; Hydrogen bromide quality percentage composition >=40% of said hydrogen bromide acetic acid solution; Said dipyridyl and verivate thereof are 2, the 2-dipyridyl; The straight-chain paraffin of said many nitrogen is a pentamethyl-diethylenetriamine; Said lower valency metal halide is cuprous bromide or ferrous bromide.
5. composite coating that is prepared from the described organosilicon of claim 1 (methyl) propenoate ABA block polymer, it is characterized in that: said composite coating is formed by following feedstock production according to the mass fraction:
6. composite coating according to claim 5; It is characterized in that: the preparation method of said (methyl) acrylic ester polymer is by following operation steps: will (methyl) acrylate monomer 20～40 mass parts, initiator 1～4 mass parts and the mixing of organic solvent 40～60 mass parts, under the vacuum condition in 70～80 ℃ of temperature stirring reaction 12～16h.
7. composite coating according to claim 6 is characterized in that: said (methyl) acrylate monomer is universal (methyl) propenoate; Said initiator is 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 4,4 '-azo (4-cyanopentanoic acid), tert-butyl peroxy acetate or peroxidized t-butyl perbenzoate; Said solvent is a toluene, 1,4-dioxane or butanone.
8. composite coating according to claim 7 is characterized in that: said universal (methyl) propenoate is more than one in (methyl) methyl acrylate and (methyl) NSC 20949.
9. composite coating according to claim 5 is characterized in that: said inorganic salt filler is white titanium pigment, talcum powder, light calcium carbonate or water-ground limestone; Said skimmer is mineral oil defoaming agent or ZGK 5 defoamer; Said dispersion agent is acrylate, polyacrylate or carboxylic acid sodium salt; Said solvent is a toluene, 1,4-dioxane or butanone.
10. the preparation method of composite coating according to claim 5; It is characterized in that comprising following operation steps: after organosilicon (methyl) propenoate ABA block polymer, (methyl) acrylic ester polymer, organic solvent, inorganic salt filler, skimmer and dispersant; In the normal temperature high speed dispersor, stir 1～3h, obtain composite coating.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1506390A (en) * | 2000-01-11 | 2004-06-23 | �������⻯ѧƷ�ع�����˾ | Macromolecule monomer comb polymer from atomic transfer free radical polymerization |
| CN1196731C (en) * | 1999-05-24 | 2005-04-13 | 荷兰联合利华有限公司 | Polysiloxane block copolymers in topical cosmetic and personal care compositions |
| CN1653101A (en) * | 2002-05-08 | 2005-08-10 | 西巴特殊化学品控股有限公司 | Polymers produced by atom transfer radical polymerisation technique with structurally modified terminal groups |
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| JP2003055419A (en) * | 2001-08-21 | 2003-02-26 | Nof Corp | Surface treatment agent for polymer material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196731C (en) * | 1999-05-24 | 2005-04-13 | 荷兰联合利华有限公司 | Polysiloxane block copolymers in topical cosmetic and personal care compositions |
| CN1506390A (en) * | 2000-01-11 | 2004-06-23 | �������⻯ѧƷ�ع�����˾ | Macromolecule monomer comb polymer from atomic transfer free radical polymerization |
| CN1653101A (en) * | 2002-05-08 | 2005-08-10 | 西巴特殊化学品控股有限公司 | Polymers produced by atom transfer radical polymerisation technique with structurally modified terminal groups |
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| JP特开2003/55419A 2003.02.26 |
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