CN1359973A - Organosilicon-modified acrylic emulsion composition and its preparing process - Google Patents
Organosilicon-modified acrylic emulsion composition and its preparing process Download PDFInfo
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- CN1359973A CN1359973A CN 00129423 CN00129423A CN1359973A CN 1359973 A CN1359973 A CN 1359973A CN 00129423 CN00129423 CN 00129423 CN 00129423 A CN00129423 A CN 00129423A CN 1359973 A CN1359973 A CN 1359973A
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Abstract
An organosilicon modified acrylic acid emulsion composition is prepared from organic polysiloxane monomer as modifier, (methyl) acrylate and functional vinyl monomer through emulsion copolymerization.
Description
The present invention relates to thermoplastic silicone modified acrylic acid emulsion and preparation method.
With (methyl) vinylformic acid and ester thereof is main raw material, utilize free-radical emulsion polymerization mechanism that organopolysiloxane is incorporated on the acrylic resin macromole, make organosilicon modified crylic acid resin, utilize Si-O bond energy big (443KJ/mol), heat, light are stablized, be not subject to action of ultraviolet ray and the characteristic of deterioration, improve performances such as resin-coated weathering resistance, salt fog resistance, temperature-change resistance, alkali resistance and oil-proofness.In addition, the organopolysiloxane macromole is the shape structure in the shape of a spiral, and methyl is outwards arranged and around the rotation of Si-O key, molecular volume is big, and force of cohesion density is low, thereby gives performances such as resin hydrophobic, anti-contamination.This resin is mainly used in the organosilicon-modified acrylic emulsion paint (being called for short silicon third emulsion paint, down together) of preparation super-weathering resistance energy as the base resin of coating, is used for decoration of exterior wall, also can be used for preparing high-grade aqueous rust-proof coatings.
Aspect the research of organosilicon modified crylic acid resin, carried out number of research projects abroad, and delivered numerous patents.As having introduced the preparation method of organosilicon-modified acrylic emulsion among patent WO5/09203, the WO95/29196, resin is made through the emulsion copolymerization reaction by methacrylic acid and ester, vinylformic acid and ester thereof, siloxanyl monomers and other vinyl monomer alkene etc.The organopolysiloxane that adopts among the patent WO95/09203 is: type siloxane polymkeric substance (methyltrimethoxy silane, Union carbide A-162 etc.); Have epoxy group(ing) (2-(3 ', 4 '-epoxy cyclohexane) ethyl trimethoxy silane, 3-(Trimethoxy silane) propyl glycidyl ether, two (2 ', 3 '-the propylene oxide hydroxypropyl) methoxy silane etc.); (3-(trimethoxysilyl) propyl group mercaptan, 3-(methyl dimethoxy oxygen base silyl) propyl group mercaptan etc.) with thio group; Have amino (3-triethoxy silyloxy propylamine, N-(3 '-trimethoxy-silylpropyl) quadrol, N-(3 '-trimethoxy-silylpropyl) urea etc.); Have halogeno-group (3-chloropropyltrimethoxy silane etc.) etc.Wherein have the good especially of epoxy group(ing).Utilize above-mentioned organopolysiloxane, carry out emulsion copolymerization, make water dispersion with excellent polymerization stability, mechanical stability and stability in storage with vinyl monomer.
The organosilicon structural table that patent WO95/29196 selects for use is shown:
R
1-Si-(R
2)
3R in the formula
1Be the aliphatic alkyl of hydrogen atom, carbonatoms 1～16, the aryl of carbonatoms 5～10, cycloalkyl, vinyl, the acrylic acid alkyl ester group of carbonatoms 1～10 or the alkyl methacrylate base of carbonatoms 1～10 of carbonatoms 5～6.Each R
2Being separately independently, can be alkoxyl group, acetoxyl or the hydroxyl of carbonatoms 1～8.
Utilize above-mentioned organopolysiloxane, patent WO95/29196 has excellent water repellency by the selection of emulsifying agent, vinyl monomer has been synthesized, water tolerance, weathering resistance, pigment-dispersing, gloss retentivity, contamination resistance, adhesive organosilicon crylic acid latex
From the patent of having reported, the organopolysiloxane monomer is introduced in the resin, the performance of emulsion and emulsion paint all is greatly improved.
The object of the invention is with a kind of organopolysiloxane macromole newly developed as one of polymerization single polymerization monomer, and itself and (methyl) vinylformic acid and esters monomer thereof are made organosilicon-modified acrylic emulsion composition through emulsion copolymerization.Purpose also is to provide the preparation method of said composition
Organosilicon-modified acrylic emulsion composition of the present invention is obtained through emulsion copolymerization by organopolysiloxane monomer, (methyl) acrylate and vinyl functional monomer raw material, it is characterized in that the monomeric molecular structure of described organopolysiloxane is:
Q=1 in the formula～5,
S＝10～60，
R
6Be CH
2=CH-or CH
2=CH (CH)
3COO (CH
2)
3-,
R
1Be methyl, ethyl, propyl group, butyl, isobutyl-or phenyl, R
1Preferable methyl,
R
2Be methyl, ethyl, propyl group, butyl, isobutyl-, phenyl or hydroxyl.
The molecular weight of this organopolysiloxane is 1000～8000, and contents of ethylene is 0.1～0.8mol/100g.
Make in the raw material of said composition, the monomeric add-on of organopolysiloxane is 1.0～30.0% of a monomer total amount, calculates in mass, and the monomer total amount is made up of the amount of organopolysiloxane and (methyl) acrylate and vinyl functional monomer.
The constitutive material of said composition is that the molecular structure of organopolysiloxane is different with the organopolysiloxane of prior art.Organopolysiloxane macromole of the present invention is a main chain with the Si-O key, gives weathering resistance, UV resistant, thermotolerance, alkali resistance of resin excellence etc.The vinyl group that contains some amount on the organopolysiloxane macromole can guarantee that organosilane monomer can be attached on the acrylic resin molecule in the mode of chemical bonding, reaches the purpose of chemical modification.The macromolecular main chain of organopolysiloxane is mainly based on methyl, gives the performance such as anti-contamination, hydrophobicity, water tolerance of coating excellence.
Except that organopolysiloxane, other polymerization single polymerization monomer: the selection of (methyl) acrylate and vinyl functional monomer, emulsifying agent, initiator is all same as the prior art.The compound emulsifying agent that emulsifying agent preferably adopts anionic emulsifier and nonionic emulsifying agent to be mixed with.Anionic emulsifier can be selected alkylsurfuric acid salt, ether sulfate class, phosphoric acid ester, Sulfonates, sulfonic acid succsinic acid salt for use.Its consumption accounts for 0.5～15%. nonionic emulsifying agent of monomer total amount can select tween series, sapn series, alkylphenol polyoxyethylene class emulsifying agent for use.Its consumption accounts for 0.5～15%. of monomer total amount
Polymerization single polymerization monomer (methyl) esters of acrylic acid can be selected (methyl) acrylate methyl esters, (methyl) acrylate ethyl ester, the positive butyl ester of (methyl) acrylate, (methyl) acrylate isobutyl ester, (methyl) acrylate 2-ethylhexyl, (methyl) acrylate ten diester etc. for use.(methyl) crylic acid hydroxy ester is as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester etc.
Functional monomer mainly is (methyl) vinylformic acid, can select for use as vinylformic acid, methacrylic acid, methylene-succinic acid and its half ester, fumaric acid and its half ester, toxilic acid and its half ester etc.Can also comprise other functional monomer such as vinylbenzene, vinyl acetate between to for plastic etc.(methyl) acrylate also belongs to the vinyl functional monomer, and the present invention tells it separately in order more clearly to describe, and is not included in the vinyl functional monomer.
Initiator can be the oxidation-reduction system that Potassium Persulphate, ammonium persulphate, persulphate and sulphite are formed.
For each monomeric amount, the monomeric add-on of organopolysiloxane is 1.0～30.0% of a monomer total amount, the amount of vinyl functional monomer is 0.1～10% of a monomer total amount, surplus is the amount of (methyl) acrylate, the ratio of soft/hard monomer is 0.5～4.0: 1.0, the emulsifying agent consumption is 1～20% of a monomer total amount, initiator amount is 0.1～5.0% of a monomer total amount, below all calculate in mass, the monomer total amount is made up of the amount of organopolysiloxane and (methyl) acrylate and vinyl functional monomer.
Preparation method of the present invention still with the processing step of prior art, comprising:
(1) the monomeric preparation of organopolysiloxane;
(2) monomer pre-emulsification technology;
(3) emulsion polymerization;
(4) aftertreatment.
The committed step of this technology is the monomeric preparation of organopolysiloxane,
Raw material is:
1, general formula is (Si (R
1R
2)-O)
nCyclosiloxane, R in the formula
1, R
2Can be methyl, ethyl, propyl group, butyl, isobutyl-, phenyl, n is 3～30,
2, general formula is: (Si (CH2=CH) m (R
3)
2n-m-O)
nVinylsiloxane, R in the formula
3Can methyl, ethyl, propyl group, butyl, isobutyl-, phenyl, n is 1～30, m be 1～60 or general formula be CH
2=CH (CH
3) COO (CH
2)
3Si (CH
3O)
3The vinyl organopolysiloxane
3, end-capping reagent: deionized water and low-molecular-weight siloxanes or polysiloxane, wherein, the general formula of low-molecular-weight siloxanes or polysiloxane is expressed as:
Si(CH
3)
3O〔-Si(R
4R
5)-O-〕
pSi(CH
3)
3
R in the formula
4, R
5Be methyl, ethyl, propyl group, butyl, isobutyl-or phenyl; P 〉=1,
4, catalyzer: catalyzer is an an acidic catalyst, and consumption is 0.1～5% or a basic catalyst of reaction raw materials total amount, and consumption is 0.1～5% of a reaction raw materials total amount.
The above-mentioned raw materials heating is reacted,
Processing condition are preferably:
The temperature of reacting by heating is 50～100 ℃, and the reaction back is warming up to 130～180 ℃, termination reaction with the deionized water wash reaction solution to neutrality or with reaction solution.
Described cyclosiloxane is preferably 1～4 kind in six alkyl cyclotrisiloxane, eight alkyl cyclotetrasiloxanes, ten alkyl D5s, dodecane basic ring six siloxanes.Also can be used with vinyl front three (second) TMOS, wherein six alkyl cyclotrisiloxane, eight alkyl cyclotetrasiloxanes are the most commonly used, and both are can arbitrary proportion composite.Other also composite with arbitrary proportion.
Vinylsiloxane has vinyl cyclotetrasiloxane, vinyl front three (second) TMOS preferably.
The usage quantity of cyclosiloxane, vinylsiloxane, end-capping reagent is a cyclosiloxane: vinylsiloxane: end-capping reagent=(76.2～86.9): (3.8～19.7): (4.1～18.6) % (m).
Catalyzer can be selected an acidic catalyst or basic catalyst for use, and an acidic catalyst is sulfuric acid, acidic white earth etc., and basic catalyst can be selected potassium hydroxide, sodium hydroxide or Tetramethylammonium hydroxide for use.
The polyreaction mode is a negatively charged ion catalytic equilibration polyreaction.
Below describe preparation method of the present invention in detail:
(1) the macromolecular preparation of organopolysiloxane
Cyclosiloxane, vinylsiloxane, end-capping reagent, catalyzer are added in the reactor, be heated to 50～100 ℃ with oil bath, insulation reaction 4～8 hours uses the deionized water wash reaction solution to neutral then, or reaction solution is warming up to 130～180 ℃, termination reaction.Vacuumize and remove light component, product is the organopolysiloxane monomer in the bottle.
(2) monomer pre-emulsification technology: anionic emulsifier and nonionic emulsifying agent are mixed with compound emulsifying agent by 1: 0.1～8 (mass ratioes), and soft/hard monomer ratio is 0.5～4.0: 1.0 (m); Function monomer accounts for 0.1～10% (m) of monomer total amount; The organopolysiloxane macromole accounts for 1.0～30.0% (m) of monomer total amount; The emulsifying agent consumption accounts for 1～20% (m) of amount of monomer; Initiator accounts for 0.1～5.0% (m) of monomer total amount. and above-mentioned mix monomer is under agitation added in the aqueous solution of emulsifying agent, make the pre-emulsion of 15～40% (m).
(3) emulsion polymerization: add the deionized water (be monomer total amount 1.5～2.5 times) of calculated amount in the reactor, be warming up to temperature of reaction, in 30～100min, above-mentioned pre-emulsion is added dropwise in the reactor insulation reaction 30～150min; With remainder polymerization single polymerization monomer in the formula ratio, in 30～100min, be added dropwise in the reactor insulation reaction 30～150min.
(4) aftertreatment: emulsion temperature is reduced to below 50 ℃,, regulate PH=7～9 with alkaline matter titration such as ammoniacal liquor, quadrols.Filter with 200 order copper mesh, obtain being with the blue light emulsion.
Advantage of the present invention:
(1) the organopolysiloxane macromole is a main chain with the Si-O key, gives weathering resistance, UV resistant, thermotolerance, alkali resistance of resin excellence etc.
(2) contain the vinyl group of some amount on the organopolysiloxane macromole, can guarantee that organosilane monomer can be attached on the acrylic resin molecule in the mode of chemical bonding, reaches the purpose of chemical modification.
(3) the macromolecular main chain of organopolysiloxane is mainly based on methyl, gives the performance such as anti-contamination, hydrophobicity, water tolerance of coating excellence.
(4) the present invention adopts pre-emulsification technology, and the polymerization process condensation product is few, and emulsion particle diameter is little, size distribution is even.
(5) the present invention makes the organosilicon crylic acid latex with nucleocapsid structure with the seeded emulsion polymerization technology, and emulsion particle diameter is little, the seepage force height; Emulsion has higher second-order transition temperature and lower minimum film-forming temperature, and the anti-after tackiness of silicon third emulsion film is good.
The present invention carries out seeded emulsion polymerization with organopolysiloxane monomer and (methyl) vinylformic acid and ester thereof and other vinyl monomer under suitable initiator effect in a word, makes the organosilicon-modified acrylic emulsion with nucleocapsid structure.It has excellent comprehensive performances.The organosilicon crylic acid latex polymerization process is stable, gel fraction＜0.5 ‰ (m); About emulsion particle diameter 50～80nm, have very little particle diameter and very narrow size distribution; Organosilicon crylic acid latex has good dilution stability, mechanical stability, package stability, freeze thaw stability.Silicon third emulsion paint with the organosilicon crylic acid latex preparation has excellent weathering resistance, alkali resistance, contamination resistance, wash-resistant property etc.For example, the UV resistant performance surpasses 1200h, not efflorescence, does not come off; In the 10%KOH aqueous solution, 24h is non-foaming, do not come off; Paint film water tolerance 4 days is no abnormal; Contamination resistance energy＜20%; Washability number of times＞10000 time.
Be embodiment below, but originally be not limited thereto:
Embodiment 1
(1) the macromolecular preparation of organopolysiloxane
In the four-hole reaction flask, add hexamethyl cyclotrisiloxane 97.4g, methyl allyl acyloxypropyl trimethoxysilane 6g, vinyl cyclotetrasiloxane 8g, deionized water 5g, potassium hydroxide (sodium hydroxide or Tetramethylammonium hydroxide) 2.5g, be heated to 50～100 ℃ with oil bath, insulation reaction 4～8 hours.Add the 100g deionized water in the reaction solution, fully stir, standing demix divides the part of anhydrating.It is neutral that repetitive scrubbing to reaction solution is.Be warming up to 130～180 ℃, vacuumize and remove light component, product is the organopolysiloxane monomer in the bottle.
(2) preparation of pre-emulsion
Beaker 1
#Middle deionized water 65g, Sodium dodecylbenzene sulfonate 3g, Voranol EP 2001 8.0g, tween 6g, the rising temperature for dissolving of adding.Take by weighing methyl methacrylate 22g in another beaker, butyl methacrylate 13g, butyl acrylate 36g, organopolysiloxane 44g, methacrylic acid 3.6g, vinylformic acid 4.8g, Potassium Persulphate 2.1g.Under whipped state, above-mentioned mix monomer is added in the aqueous solution of emulsifying agent, be uniformly dispersed, make pre-emulsion.
At beaker 2
#Middle methyl methacrylate 76.5g, methacrylic ester 2-ethylhexyl 48.2g, the butyl acrylate 71.8g of adding forms mixing solutions.
(3) preparation of organosilicon crylic acid latex
Having reflux exchanger, adding deionized water 250g in the four-hole reaction flask of agitator, dropping funnel, thermometer, be warming up to 70～90 ℃, in 30～100min, beaker 1
#In pre-emulsion be added dropwise in the reactor insulation reaction 30～150min; With mix monomer, in 30～100min, be added dropwise in the reactor insulation reaction 30～150min.Cooling.Under whipped state,, filter to PH=7～9 with ammonia water titration the said products with 200 order copper wire gauze, make organosilicon crylic acid latex.Monomer conversion 99.2%, yield 99.1%, solid content 50.2%
Embodiment 2
In the four-hole reaction flask, add hexamethyl cyclotrisiloxane 92.7g, vinyl cyclotetrasiloxane 24g, deionized water 5g, Tetramethylammonium hydroxide 5.5g, be heated to 50～100 ℃ with oil bath, insulation reaction 4～8 hours.Be warming up to 150 ℃ then, termination reaction vacuumizes and removes light component, and product is the organopolysiloxane monomer in the bottle.
Add deionized water 65g, Sodium dodecylbenzene sulfonate 3g, Voranol EP 2001 8.0g, tween 6g, rising temperature for dissolving in the beaker.Take by weighing methyl methacrylate 22g in another beaker, Propenoic acid, 2-methyl, isobutyl ester 13g, butyl acrylate 36g, organopolysiloxane 44g, methacrylic acid 3.6g, vinylformic acid 4.8g, Potassium Persulphate 2.1g.Under high-speed stirring, above-mentioned mix monomer is added in the aqueous solution of emulsifying agent, be uniformly dispersed, make pre-emulsion.Other prescription and technology are with embodiment 1.Monomer conversion 99.4%, its yield 97.9%, solid content 50%.
Embodiment 3
In the preparation of pre-emulsion,, add deionized water 65 grams, sodium lauryl sulphate 3g among the beaker 1#, tridecyl alcohol ethoxylate 7.2g, sapn 8.1g, rising temperature for dissolving as embodiment 1.Other prescription and technology are identical with embodiment 1.Monomer conversion 99.8%, its yield 98.1%, solid content 49.5%
Embodiment 4
In the preparation of pre-emulsion, as embodiment 2, take by weighing methyl methacrylate 22g in another beaker, methacrylic ester ten diester 23g, butyl acrylate 36g, organopolysiloxane 44g, methacrylic acid 6.6g, Potassium Persulphate 6.1g.Under high-speed stirring, above-mentioned mix monomer is added in the aqueous solution of emulsifying agent, be uniformly dispersed, make pre-emulsion.Other prescription and technology are with embodiment 2.Monomer conversion 99.7%, its yield 97.9%, solid content 50%.
Embodiment 5
In the preparation of pre-emulsion, as embodiment 2, take by weighing methyl methacrylate 22g in another beaker, butyl methacrylate 23g, glycidyl methacrylate 6g, organopolysiloxane 44g, vinylformic acid 6.6g, ammonium persulphate 4.1g.Under high-speed stirring, above-mentioned mix monomer is added in the aqueous solution of emulsifying agent, be uniformly dispersed, make pre-emulsion.Other prescription and technology are with embodiment 1.Monomer conversion 99.2%, its yield 97.9%, solid content 50%.
Embodiment 6
In the four-hole reaction flask, add octaphenyl cyclotetrasiloxane 441.7g, vinyl cyclotetrasiloxane 24g, hexamethyldisiloxane 42.2g, Tetramethylammonium hydroxide 2.5g, be heated to 50～100 ℃ with oil bath, insulation reaction 4～8 hours, be warming up to 150 ℃ then, termination reaction, vacuumize and remove light component, product is an organopolysiloxane in the bottle.
Pre-emulsification of monomer and polymerization technique be with embodiment 1, monomer conversion 99.3%, yield 99.5%, solid content 49.8%.
Embodiment 7
In the four-hole reaction flask, add hexamethyl cyclotetrasiloxane 64.8g, octamethylcyclotetrasiloxane 55.5g, vinyl cyclotetrasiloxane 24g, hexamethyldisiloxane 42.2g, Tetramethylammonium hydroxide 2.5g, be heated to 50～100 ℃ with oil bath, insulation reaction 4～8 hours, be warming up to 150 ℃ then, termination reaction, vacuumize and remove light component, product is an organopolysiloxane in the bottle.
Pre-emulsification of monomer and polymerization technique be with embodiment 1, monomer conversion 99.3%, yield 99.4%, solid content 49.9%.
Embodiment 8
In the four-hole reaction flask, add octamethylcyclotetrasiloxane 176.8g, vinyltriethoxysilane 8.8g, hexamethyldisiloxane 42.2g, Tetramethylammonium hydroxide 2.5g, be heated to 50～100 ℃ with oil bath, insulation reaction 4～8 hours adds the 100g deionized water then in the reaction solution, fully stir, standing demix, branch vibration layer, repetitive scrubbing is warming up to 130～180 ℃ to neutral, vacuumize and remove light component, product is an organopolysiloxane in the bottle.
Pre-emulsification of monomer and polymerization technique be with embodiment 1, monomer conversion 99.5%, yield 99.3%, solid content 49.8%.
Comparative Examples 1
Methyl methacrylate 28g, butyl methacrylate 23g, butyl acrylate 11g, vinylformic acid 6.6g, ammonium persulphate 4.1g.Under high-speed stirring, above-mentioned mix monomer is added in the aqueous solution of emulsifying agent, be uniformly dispersed, make pre-emulsion.Other prescription and technology are with embodiment 1.Monomer conversion 99.5%, its yield 98.9%, solid content 50%.
Comparative Examples 2
Methyl methacrylate 28g, vinylbenzene 12g, butyl acrylate 41g, vinylformic acid 6.6g, ammonium persulphate 4.1g.Under high-speed stirring, above-mentioned mix monomer is added in the aqueous solution of emulsifying agent, be uniformly dispersed, make pre-emulsion.Other prescription and technology are with embodiment 1.Monomer conversion 99.4%, its yield 99.7%, solid content 50%.
Auxiliary agents such as wetting agent, dispersion agent, anticorrosion and bactericidal agent, thickening material, defoamer are disperseed, grind with pigment, filler; Under whipped state, organosilicon crylic acid latex is slowly added; Add remaining sterilant etc.; Regulate viscosity with deionized water, thickening material, 120 order stainless (steel) wires filter, and make silicon third emulsion paint.
Get the cement asbestos model of 150mm * 70mm, in tap water, soak 48h, remove alkalescence.With 0
#Sand paper is polished repeatedly, removes surface dirt, and is clean with flushing with clean water again, dries.Adopt and brush technology, make silicon third emulsion film.The organosilicon crylic acid latex performance index see Table 1, and the silicon third latex film performance sees Table 2.
Table 1 organosilicon crylic acid latex performance index
| Sequence number | Particle diameter (nm) | Chemical electrolysis matter stability | Mechanical stability | Dilution stability | ||
| ?Z | ?N | ?M | ||||
| Embodiment 1 | ?52.9 | ?43.0 | ?49.9 | By | By | By |
| Embodiment 2 | ?52.3 | ?42.7 | ?48.7 | By | By | By |
| Embodiment 3 | ?67.6 | ?60.6 | ?70.4 | By | By | By |
| Embodiment 4 | ?56.3 | ?47.9 | ?53.9 | By | By | By |
| Embodiment 5 | ?52.0 | ?36.8 | ?45.1 | By | By | By |
| Comparative Examples 1 | ?72.4 | ?66.1 | ?68.2 | By | By | By |
| Comparative Examples 2 | ?85.3 | ?67.2 | ?76.1 | By | By | By |
The table 2 silicon third emulsion film performance
| Sequence number | The washability number of times | Contamination resistance | Pendulum-rocker hardness | Water tolerance | Alkali resistance 10%KOH solution | Temperature-change resistance (20 times) |
| Embodiment 1 | ＞10000 | ?11.4％ | 0.54 | ＞96h | ?＞24h | By |
| Embodiment 2 | ＞10000 | ?15.2％ | 0.53 | ＞96h | ?＞24h | By |
| Embodiment 3 | ＞10000 | ?12.3％ | 0.49 | ＞96h | ?＞24h | By |
| Embodiment 4 | ＞10000 | ?8.8％ | 0.51 | ＞96h | ?＞24h | By |
| Embodiment 5 | ＞10000 | ?15.4％ | 0.49 | ＞96h | ?＞24h | By |
| Comparative Examples 1 | 8000 | ?17.6％ | 0.51 | ＞96h | ?＞24h | By |
| Comparative Examples 2 | 8000 | ?18.8％ | 0.49 | ＞96h | ?＞24h | By |
Claims (11)
1, a kind of organosilicon-modified acrylic emulsion composition is obtained through emulsion copolymerization by organopolysiloxane monomer, (methyl) acrylate and vinyl functional monomer raw material, it is characterized in that the monomeric molecular structure of described organopolysiloxane is:
Q=1 in the formula～5,
S＝10～60，
R
6Be CH
2=CH-or CH
2=CH (CH)
3COO (CH
2)
3-,
R
1Be methyl, ethyl, propyl group, butyl, isobutyl-or phenyl,
R
2Be methyl, ethyl, propyl group, butyl, isobutyl-, phenyl or hydroxyl.
2, composition according to claim 1 is characterized in that R
1Be methyl.
3, composition according to claim 1, the molecular weight that it is characterized in that described organopolysiloxane is 1000～8000, contents of ethylene is 0.1～0.8mol/100g.
4, composition according to claim 1, it is characterized in that the monomeric add-on of organopolysiloxane is 1.0～30.0% of a monomer total amount, calculate in mass, the monomer total amount is made up of the amount of organopolysiloxane, (methyl) acrylate and vinyl functional monomer.
5, composition according to claim 1, it is characterized in that the monomeric add-on of organopolysiloxane is 1.0～30.0% of a monomer total amount, the amount of vinyl functional monomer is 0.1～10% of a monomer total amount, surplus is the amount of (methyl) acrylate, the ratio of soft/hard monomer is 0.5～4.0: 1.0, the emulsifying agent consumption is 1～20% of a monomer total amount, initiator amount is 0.1～5.0% of a monomer total amount, below all calculate in mass, the monomer total amount is made up of the amount of organopolysiloxane, (methyl) acrylate and vinyl functional monomer.
6, a kind of method for preparing the described organosilicon-modified acrylic emulsion composition of claim 1 comprises:
(1) the monomeric preparation of organopolysiloxane;
(2) monomer pre-emulsification technology;
(3) emulsion polymerization;
(4) aftertreatment,
It is characterized in that:
(1) the monomeric preparation of organopolysiloxane:
Raw material is:
General formula is (Si (R
1R
2)-O)
nCyclosiloxane, R in the formula
1, R
2Can be methyl, ethyl, propyl group, butyl, isobutyl-, phenyl, n is 3～30,
General formula is: (Si (CH2=CH) m (R
3)
2n-m-O)
nVinylsiloxane, R in the formula
3Can methyl, ethyl, propyl group, butyl, isobutyl-, phenyl, n is 1～30, m be 1～60 or general formula be CH
2=CH (CH
3) COO (CH
2)
3Si (CH
3O)
3The vinyl organopolysiloxane
End-capping reagent: deionized water and low-molecular-weight siloxanes or polysiloxane, wherein, the general formula of low-molecular-weight siloxanes or polysiloxane is expressed as:
Si(CH
3)
3O〔-Si(R
4R
5)-O-〕
pSi(CH
3)
3
R in the formula
4, R
5Be methyl, ethyl, propyl group, butyl, isobutyl-or phenyl; P 〉=1,
And catalyzer carries out reacting by heating, and catalyzer is an an acidic catalyst, and consumption is 0.1～5% or a basic catalyst of reaction raw materials total amount, and consumption is 0.1～5% of a reaction raw materials total amount;
7, method according to claim 6 is characterized in that:
(1) organopolysiloxane monomer preparation: the temperature of reacting by heating is 50～100 ℃, and the reaction back is warming up to 130～180 ℃, termination reaction with the deionized water wash reaction solution to neutrality or with reaction solution.
8, method according to claim 6 is characterized in that:
(1) organopolysiloxane monomer preparation:
Described cyclosiloxane is 1～4 kind in six alkyl cyclotrisiloxane, eight alkyl cyclotetrasiloxanes, ten alkyl D5s, dodecane basic ring six siloxanes,
Vinylsiloxane is vinyl cyclotetrasiloxane, vinyl front three (second) TMOS.
9, method according to claim 6 is characterized in that the molecular weight of the organopolysiloxane that makes is 1000～8000, and the content of vinyl is 0.1～0.8mol/100g.
10, method according to claim 6, the usage quantity that it is characterized in that cyclosiloxane, vinylsiloxane, end-capping reagent is a cyclosiloxane: vinylsiloxane: end-capping reagent=(76.2～86.9): (3.8～19.7): (4.1～18.6) % (m).
11, method according to claim 6 is characterized in that:
(2) monomer pre-emulsification technology: the raw material of letex polymerization made 15～40% pre-emulsion;
(3) emulsion polymerization: under 70～90 ℃ of temperature of reaction, pre-emulsion was added dropwise to the deionized water insulation reaction 30～150 minutes, remaining polymerization single polymerization monomer in the formula ratio is added, under 70～90 ℃ of temperature of reaction, reacted 30～150 minutes.
(4) aftertreatment: reduce emulsion temperature, regulating PH is 7～9, filters and obtains being with the blue light emulsion.
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| CN100381484C (en) * | 2005-03-04 | 2008-04-16 | 华东理工大学 | Process for preparing core-shell type polysiloxane composite particles |
| CN101768316A (en) * | 2010-03-04 | 2010-07-07 | 陕西科技大学 | Preparation method of polyaniline/P (MMA-BA-HEA) conductive composite material |
| CN110452341A (en) * | 2019-09-03 | 2019-11-15 | 铨盛聚碳科技股份有限公司 | A kind of organosilicon toughener and preparation method thereof of emulsion-suspension polymerization synthesis |
| CN115746633A (en) * | 2022-11-14 | 2023-03-07 | 西安元创化工科技股份有限公司 | Water-based PTP aluminum foil OP protective agent and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100381484C (en) * | 2005-03-04 | 2008-04-16 | 华东理工大学 | Process for preparing core-shell type polysiloxane composite particles |
| CN101768316A (en) * | 2010-03-04 | 2010-07-07 | 陕西科技大学 | Preparation method of polyaniline/P (MMA-BA-HEA) conductive composite material |
| CN101768316B (en) * | 2010-03-04 | 2011-09-14 | 陕西科技大学 | Preparation method of polyaniline/P (MMA-BA-HEA) conductive composite material |
| CN110452341A (en) * | 2019-09-03 | 2019-11-15 | 铨盛聚碳科技股份有限公司 | A kind of organosilicon toughener and preparation method thereof of emulsion-suspension polymerization synthesis |
| CN110452341B (en) * | 2019-09-03 | 2022-02-22 | 铨盛（云浮）新型聚合物有限公司 | Organosilicon toughening agent synthesized by emulsion-suspension polymerization method and preparation method thereof |
| CN115746633A (en) * | 2022-11-14 | 2023-03-07 | 西安元创化工科技股份有限公司 | Water-based PTP aluminum foil OP protective agent and preparation method thereof |
| CN115746633B (en) * | 2022-11-14 | 2024-04-02 | 西安元创化工科技股份有限公司 | Water-based PTP aluminum foil OP protective agent and preparation method thereof |
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