CN101575398B - Organosilicon-modified acrylate emulsion and preparation method of coating agent for powder-free gloves - Google Patents
Organosilicon-modified acrylate emulsion and preparation method of coating agent for powder-free gloves Download PDFInfo
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- CN101575398B CN101575398B CN200910069162XA CN200910069162A CN101575398B CN 101575398 B CN101575398 B CN 101575398B CN 200910069162X A CN200910069162X A CN 200910069162XA CN 200910069162 A CN200910069162 A CN 200910069162A CN 101575398 B CN101575398 B CN 101575398B
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Abstract
The invention relates to an organosilicon-modified acrylate emulsion and a preparation method of a coating agent for powder-free gloves. The preparation method comprises the following steps of: preparing the organosilicone-modified acrylate emulsion; adding the organosilicon-modified acrylate emulsion into a stirred tank; adding a wetting agent for base materials, a germicide and deionized water under constant mixing; then adding a foam killer, a thickening agent, a pH value conditioner after evenly mixing; and discharging after evenly mixing. The solid content of the coating agent of the organosilicon-modified acrylate emulsion is between 10% and 30%; the surface tension is not more than 35mN/m; and the viscosity is between 100 mPa.s and 1000mPa.s; and the pH value is between 7 and 9. Thecoating agent is diluted with the deionized water according to a rate of 1:19, is leached by a hand model coated with a disposable glove and then is dried at the temperature between 100 DEG C and 150 DEG C. Finally the powder-free gloves processed by the coating agent are formed after demolding.
Description
Technical field
The present invention relates to a kind of organosilicon-modified acrylate emulsion and be used to make the preparation method of the finishing agent of powder-free gloves, can be used for making all kinds of powder-free gloves.
Background technology
Disposable glove such as natural rubber gloves, acrylonitrile butadiene glove and PVC gloves etc. have a wide range of applications in productive life and medical field.Yet because the character of macromolecular material itself, if do not carry out surface treatment, the internal surface of these disposable gloves is easy to adhesion, can't take off from fingerprint, promptly allows to demoulding gloves and glues in also can taking place and can't dress.Therefore in gloves were produced, it was a very important step that the gloves internal surface is carried out surface treatment.
Traditional surface-treated method is to be coated with powder materials such as one deck starch, talcum powder at the gloves internal surface, but these powder materials come off easily, cause wound infection easily at medical field, then pollute circuit etc. easily in electron trade, limit the range of application of disposable glove, thereby needed the adversary to overlap not have efflorescence to handle.The method that no efflorescence is handled has two classes, and the first kind is a chloridization process, but this method causes environmental pollution easily; Second class is to cover with paint, lacquer, colour wash, etc. one deck polymeric coating layer at the gloves internal surface, and it is better to obtain smooth degree, is difficult for the gloves of adhesion.For example patent CN1195607A (publication number) has introduced the method that a kind of double-steeping polyaminoester emulsion is produced the PVC powder-free gloves, and patent CN101194862A (publication number) has introduced the method with elastic polyurethane coated natural Rubber gloves internal surface.The finishing agent of this polyurethanes often needs to add mineral filler or dystectic organic filler to increase the smooth property and the resistance to blocking of coating, and cost is higher, and does not often reach smooth effect of ideal and ageing resistance.In addition, finishing agent will be on the surface of low surface energies such as PVC spreading wetting, need very low surface tension, adopt the polyurethanes finishing agent often bright spot to occur at the gloves internal surface because surface tension is low inadequately, coating is inhomogeneous.
Summary of the invention
In view of above situation, we investigate to current material and study, and find that the acrylic ester emulsion film forming is plentiful even, are widely used at coating and leather finish field, and polyacrylic ester also has the shortcoming of self simultaneously, as hot sticky cold crisp.Si-O bond energy (450kJ/mol) is much larger than C-C bond energy (345kJ/mol) in the organosilicon, therefore in acrylate resin, introduce the resistant of high or low temperature that Si-O can effectively improve matrix resin, improve the resistance to bond of polyacrylic ester film, Si-O is better flexible simultaneously, can improve the feel of filming, organosilyl surface tension is extremely low, can increase the spreading ability of emulsion on the low surface energy surface, obtains even flawless coating.
The present invention adopts organosilicon that acrylate resin is carried out modification, and then adopts this organosilicon-modified acrylate emulsion to make finishing agent.Utilize this finishing agent to make powder-free gloves, shortcomings such as coating is inhomogeneous to improve, defectiveness and gloves resistance to blocking, smooth property, poor water resistance can reduce the cost of finishing agent simultaneously.
Concrete technical scheme of the present invention is as follows:
The preparation method of machine fluorine-silicon modified acrylic ester emulsion of the present invention, its raw material composition and mass fraction proportioning are as follows:
65～92 parts of acrylate
5～20 parts of function monomers
3～15 parts of organosilane monomers
1.5～7 parts of emulsifying agents
0.2～2 part of initiator
0.5～3 part of pH value buffer reagent
80～400 parts of deionized waters;
Its preparation method is as follows:
(1) preparation of stratum nucleare
Take by weighing that 40%～60% emulsifying agent and whole pH value buffer reagent are dissolved in 40%～50% deionized water and place reactor in the prescription, under continue stirring, the mix monomer that 40%～70% acrylate and 40%～70% function monomer are formed adds in the reactor emulsification to forming stable emulsion and being warming up to 65～70 ℃; Initiator is dissolved in 30%～40% deionized water and gets 40%～60% initiator solution and add reactor and begin reaction, be warming up to 75～85 ℃ gradually, reaction 1.5～2h promptly gets the stratum nucleare emulsion;
(2) preparation of organosilicon-modified acrylate emulsion
The remainder emulsifying agent is dissolved in the residue deionized water, adds whole organosilane monomers and remainder acrylate, function monomer stirring and emulsifying to forming stable pre-emulsion; Continue reaction in the stratum nucleare emulsion with being added dropwise in this pre-emulsion and the remainder initiator solution 1～1.5h, keep 75～85 ℃ of temperature of reaction, be added dropwise to complete back sustained reaction 1h; Be cooled to 30～50 ℃, regulate pH=7～9 dischargings with ammoniacal liquor.
Described acrylate is two or more the mixture at least in methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, Isooctyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate or the Isooctyl acrylate monomer.Wherein the homopolymer glass transition temperature of methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate and Isooctyl methacrylate is higher, belongs to the hard monomer class; The second-order transition temperature of methyl acrylate, ethyl propenoate, butyl acrylate and Isooctyl acrylate monomer is lower, belongs to the soft monomer class.The soft or hard monomer at least respectively selects a kind of or respectively selects multiple and resize ratio makes the emulsion can be 100～150 ℃ of following film forming and unlikely being clamminess.
Described function monomer is the mixture more than at least three kinds or three kinds in vinylformic acid, methacrylic acid, vinyl cyanide, 2-Hydroxy ethyl acrylate, vinylformic acid-2-hydroxy propyl ester, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester, glycol ether diacrylate, methylene-bisacrylamide or the Vinylstyrene.Wherein vinylformic acid, methacrylic acid and vinyl cyanide can improve the sticking power between resin and base material; 2-Hydroxy ethyl acrylate, vinylformic acid-2-hydroxy propyl ester, methacrylic acid-2-hydroxy methacrylate and methacrylic acid-2-hydroxy propyl ester provide can with the crosslinked hydroxyl that reacts such as carboxyl, hydroxyl; Glycol ether diacrylate, methylene-bisacrylamide and Vinylstyrene then belong to the bifunctional crosslinking agent.This three classes monomer at least respectively selects one or respectively selects multiple.
Described organosilane monomer is that vinyltrimethoxy silane, vinyltriethoxysilane, vinyl methoxyl group diethoxy silane, gamma-methyl allyl acyloxypropyl trimethoxysilane or relative molecular mass are a kind of in 1000～2000 the vinyl silicone oil.
Described emulsifying agent is the mixed emulsifier of nonionic emulsifying agent and anionic emulsifier collocation, the ratio of nonionic emulsifying agent and anionic emulsifier is between 1: 1～3: 1, preferred 2: 1, nonionic emulsifying agent comprises alkylphenol polyoxyethylene, polyoxyethylene sorbitan fatty acid ester, anionic emulsifier such as sodium lauryl sulphate, Sodium dodecylbenzene sulfonate.
Described initiator is ammonium persulphate, Sodium Persulfate or Potassium Persulphate; Described pH value buffer reagent is a sodium bicarbonate.
Machine fluorine-silicon modified acrylic ester emulsion is used to make the preparation method of the finishing agent of powder-free gloves, and the composition and the mass fraction of organosilicon-modified acrylate finishing agent are as follows:
40～80 parts of organosilicon-modified acrylate emulsions
0.5～5 part of base material wetting agent
0.05～1 part of defoamer
1～6 part of thickening material
0.1～3 part of pH value conditioning agent
0.5～3 part in sterilant
10～60 parts of deionized waters;
Organosilicon-modified acrylate emulsion is added in the stirring tank, continuing to add base material wetting agent, sterilant, deionized water successively under the stirring, add defoamer, thickening material, pH value conditioning agent after stirring again successively, the back discharging that stirs gets final product.
Described base material wetting agent is the organic silicon modified by polyether class, the preferred high auxiliary agent of enlightening (Germany, Tego) Wet KL245, Wet260, Bi Ke chemistry (Germany, BYK-Chemie) BYK-348, BYK-349.
Described defoamer is silicone based, the preferred high auxiliary agent Foamex808 of enlightening, Foamex810, Foamex815N; Described thickening material is an association type alkali swelling class, preferably Kening Co.,Ltd (Germany, Cognis) HAS662, HAS634.
Described pH value conditioning agent is a kind of in ammoniacal liquor, 2-amino-2-methyl-1-propanol, the quadrol; Described sterilant is the card pine.
The organosilicon-modified acrylate finishing agent solid content of the present invention preparation between 10%～30%, preferred 15%～25%; Surface tension≤35mN/m, preferred≤30mN/m; Viscosity 100～1000mPas, preferred 200～500mpas; PH value 7～9.With this finishing agent and deionized water by dilution in 1: 19 after, with the fingerprint leaching finishing agent that scribbles disposable glove, 100～150 ℃ of oven dry down, the demoulding promptly obtains the powder-free gloves with this finishing agent processing.The gloves that make are done following test:
(1) resistance to bond
Gloves are placed 70 ℃ of baking ovens, needed time when observation gloves inside sticks together.
(2) smooth property
With the wearable property of feel official gloves, smooth property.
(3) water tolerance
Whether the gloves water-filling done hang water test, water is poured out after hanging water 1h, observing coating has obscission.
Through test, with the every excellent performance of gloves that finishing agent of the present invention is made, every index is all above commercially available finishing agent product, and cost is lower, alternative existing finishing agent product.
Embodiment
Further specify the present invention below in conjunction with specific embodiment, but the present invention is not limited to following example.
Embodiment 1
One, organosilicon-modified acrylate emulsion preparation
Employed concrete raw material and mass fraction proportioning are as follows:
42 parts of methyl methacrylates
25 parts of ethyl propenoates
10 parts of butyl acrylates
4 parts of 2-Hydroxy ethyl acrylates
10 parts of vinyl cyanide
4 parts in vinylformic acid
2 parts of glycol ether diacrylates
3 parts of vinyltrimethoxy silanes
1 part in Nonyl pheno (10) ether
0.5 part of sodium lauryl sulphate
0.2 part of ammonium persulphate
0.5 part of sodium bicarbonate
80 parts of deionized waters
(1) preparation of stratum nucleare
Taking by weighing 0.6 part of polyoxyethylene nonylphenol ether, 0.3 part of sodium lauryl sulphate and 0.5 part of sodium bicarbonate is dissolved in 35 parts of deionized waters and places reactor, under continue stirring, the mix monomer that 25 parts of methyl methacrylates, 17 parts of ethyl propenoates, 7 parts of butyl acrylates and 3 parts of 2-Hydroxy ethyl acrylates, 4 parts of vinyl cyanide, 3 parts of vinylformic acid, 1.5 parts of glycol ether diacrylates are formed adds in the reactor emulsification to forming stable emulsion and being warming up to 65～70 ℃.0.2 part of initiator is dissolved in 25 parts of water and gets 60% initiator solution and add reactor and begin reaction, be warming up to 75 ℃ gradually, reaction 2h promptly gets the stratum nucleare emulsion, and control reaction temperature is 75～77 ℃ in the reaction process.
(2) preparation of organosilicon-modified acrylate emulsion
The remainder emulsifying agent is dissolved in the residue deionized water, adds whole vinyltrimethoxy silanes and remainder methyl methacrylate, ethyl propenoate, butyl acrylate, 2-Hydroxy ethyl acrylate, vinyl cyanide, vinylformic acid, glycol ether diacrylate stirring and emulsifying to forming stable pre-emulsion.Continue reaction in the stratum nucleare emulsion with being added dropwise in this pre-emulsion and the remainder initiator solution 1h, keep 75～77 ℃ of temperature of reaction, be added dropwise to complete back sustained reaction 1h.Be cooled to 30～50 ℃, regulate pH=7～9 dischargings with ammoniacal liquor.
Two, the preparation of organosilicon-modified acrylate finishing agent
Its composition and mass fraction are as follows:
40 parts of embodiment 1 emulsions
1.5 parts of WetKL245
0.3 part of Foamex815N
3 parts of HAS662
1 part of ammoniacal liquor
0.5 part of card pine
53.7 parts of deionized waters;
Embodiment 1 emulsion is added in the stirring tank, add Wet KL245, card pine, deionized water successively under continuing to stir, carry after stirring and add Foamex815N, HAS662, ammoniacal liquor more successively, the back discharging that continues to stir gets 100 parts of finishing agents.Gained finishing agent solid content is 25%, surface tension 28.7mN/m, viscosity 310mPas, pH value 7.8.
Embodiment 2
One, organosilicon-modified acrylate emulsion preparation
Employed concrete raw material and mass fraction proportioning are as follows:
50 parts of methyl methacrylates
10 parts of Jia Jibingxisuanyizhis
20 parts of ethyl propenoates
2.5 parts in vinylformic acid-2-hydroxy propyl ester
2 parts in vinylformic acid
0.5 part of glycol ether diacrylate
15 parts of vinyltriethoxysilanes
1.5 parts in Nonyl pheno (10) ether
1.5 parts of Sodium dodecylbenzene sulfonatees
1 part of Potassium Persulphate
3 parts of sodium bicarbonates
150 parts of deionized waters
(1) preparation of stratum nucleare
Taking by weighing 0.6 part of polyoxyethylene nonylphenol ether, 0.6 part of Sodium dodecylbenzene sulfonate and 3 parts of sodium bicarbonates is dissolved in 65 parts of deionized waters and places reactor, under continue stirring, the mix monomer that 24 parts of methyl methacrylates, 4 parts of Jia Jibingxisuanyizhis, 9.5 parts of ethyl propenoates and 1 part of vinylformic acid-2-hydroxy propyl ester, 1 part of vinylformic acid, 0.3 part of glycol ether diacrylate are formed adds in the reactor emulsification to forming stable emulsion and being warming up to 65～70 ℃.1 part of Potassium Persulphate is dissolved in 50 parts of water and gets 40% its solution and add reactor and begin reaction, be warming up to 80 ℃ gradually, reaction 1.5h promptly gets the stratum nucleare emulsion, and control reaction temperature is 79～81 ℃ in the reaction process.
(2) preparation of organosilicon-modified acrylate emulsion
The remainder emulsifying agent is dissolved in the residue deionized water, adds whole vinyltriethoxysilanes and remainder methyl methacrylate, Jia Jibingxisuanyizhi, ethyl propenoate, vinylformic acid-2-hydroxy propyl ester, vinylformic acid, glycol ether diacrylate stirring and emulsifying to forming stable pre-emulsion.Continue reaction in the stratum nucleare emulsion with being added dropwise in this pre-emulsion and the remainder initiator solution 1.5h, keep 79～81 ℃ of temperature of reaction, be added dropwise to complete back sustained reaction 1h.Be cooled to 30～50 ℃, regulate pH=7～9 dischargings with ammoniacal liquor.
Two, the preparation of organosilicon-modified acrylate finishing agent
Its composition and mass fraction are as follows:
50 parts of embodiment 2 emulsions
0.5 part of WetKL245
0.05 part of Foamex810
1 part of HAS662
0.1 part of 2-amino-2-methyl-1-propanol
3 parts of card pines
45.35 parts of deionized waters;
Embodiment 2 emulsions are added in the stirring tank, continuing to add Wet KL245, card pine, deionized water under the stirring successively, carry after stirring and add Foamex810, HAS662,2-amino-2-methyl-1-propanol more successively, the back discharging that continues to stir gets 100 parts of finishing agents.Gained finishing agent solid content is 21.5%, surface tension 29.5mN/m, viscosity 230mPas, pH value 7.5.
Embodiment 3
One, organosilicon-modified acrylate emulsion preparation
Employed concrete raw material and mass fraction proportioning are as follows:
52 parts of methyl methacrylates
10 parts of methyl acrylates
30 parts of ethyl propenoates
2 parts of 2-Hydroxy ethyl acrylates
2 parts of methacrylic acids
1 part of methylene-bisacrylamide
3 parts of gamma-methyl allyl acyloxypropyl trimethoxysilanes
4.5 parts of polyoxyethylene (20) sorbitan monooleates
1.5 parts of Sodium dodecylbenzene sulfonatees
2 parts of Sodium Persulfates
1 part of sodium bicarbonate
200 parts of deionized waters
(1) preparation of stratum nucleare
Taking by weighing 2.3 parts of polyoxyethylene (20) sorbitan monooleate, 0.8 part of Sodium dodecylbenzene sulfonate and 1 part of sodium bicarbonate is dissolved in 90 parts of deionized waters and places reactor, under continue stirring, the mix monomer that 27 parts of methyl methacrylates, 5 parts of methyl acrylates, 16 parts of ethyl propenoates and 1 part of 2-Hydroxy ethyl acrylate, 1 part of methacrylic acid, 0.5 part of methylene-bisacrylamide are formed adds in the reactor emulsification to forming stable emulsion and being warming up to 65～70 ℃.2 parts of Sodium Persulfates are dissolved in 70 parts of water and get 50% its solution and add reactor and begin reaction, be warming up to 85 ℃ gradually, reaction 1.7h promptly gets the stratum nucleare emulsion, and control reaction temperature is 83～85 ℃ in the reaction process.
(2) preparation of organosilicon-modified acrylate emulsion
The remainder emulsifying agent is dissolved in the residue deionized water, adds whole gamma-methyl allyl acyloxypropyl trimethoxysilanes and remainder methyl methacrylate, methyl acrylate, ethyl propenoate, 2-Hydroxy ethyl acrylate, methacrylic acid, methylene-bisacrylamide stirring and emulsifying to forming stable pre-emulsion.Continue reaction in the stratum nucleare emulsion with being added dropwise in this pre-emulsion and the remainder initiator solution 1.3h, keep 83～85 ℃ of temperature of reaction, be added dropwise to complete back sustained reaction 1h.Be cooled to 30～50 ℃, regulate pH=7～9 dischargings with ammoniacal liquor.
Two, the preparation of organosilicon-modified acrylate finishing agent
Its composition and mass fraction are as follows:
45 parts of embodiment 3 emulsions
260 5 parts of Wet
1 part of Foamex808
6 parts of HAS634
3 parts of quadrols
1.5 parts of card pines
38.5 parts of deionized waters;
Embodiment 3 emulsions are added in the stirring tank, add Wet 260, card pine, deionized water successively under continuing to stir, carry after stirring and add Foamex808, HAS634, quadrol more successively, the back discharging that continues to stir gets 100 parts of finishing agents.Gained finishing agent solid content is 23.5%, surface tension 27mN/m, viscosity 500mPas, pH value 8.1.
Embodiment 4
One, organosilicon-modified acrylate emulsion preparation
Employed concrete raw material and mass fraction proportioning are as follows:
40 parts of methyl methacrylates
25 parts of ethyl propenoates
9 parts of vinyl cyanide
4 parts of methacrylic acids-2-hydroxy methacrylate
4 parts in vinylformic acid
3 parts of methylene-bisacrylamides
15 parts of vinyl silicone oils
4.7 parts in Nonyl pheno (10) ether
2.3 parts of sodium lauryl sulphate
1 part of ammonium persulphate
1.5 parts of sodium bicarbonates
300 parts of deionized waters
(1) preparation of stratum nucleare
Taking by weighing 1.9 parts of polyoxyethylene nonylphenol ethers, 0.9 part of sodium lauryl sulphate and 1.5 parts of sodium bicarbonates is dissolved in 150 parts of deionized waters and places reactor, under continue stirring, the mix monomer that 22 parts of methyl methacrylates, 11 parts of ethyl propenoates and 4 parts of vinyl cyanide, 1.5 parts of methacrylic acid-2-hydroxy methacrylates, 1.5 parts of vinylformic acid, 1 part of methylene-bisacrylamide are formed adds in the reactor emulsification to forming stable emulsion and being warming up to 65～70 ℃.1 part of ammonium persulphate is dissolved in 90 parts of water and gets 40% its solution and add reactor and begin reaction, be warming up to 80 ℃ gradually, reaction 1.5h promptly gets the stratum nucleare emulsion, and control reaction temperature is 79～81 ℃ in the reaction process.
(2) preparation of organosilicon-modified acrylate emulsion
The remainder emulsifying agent is dissolved in the residue deionized water, adds whole vinyl silicone oils and remainder methyl methacrylate, ethyl propenoate, vinyl cyanide, methacrylic acid-2-hydroxy methacrylate, vinylformic acid, methylene-bisacrylamide stirring and emulsifying to forming stable pre-emulsion.Continue reaction in the stratum nucleare emulsion with being added dropwise in this pre-emulsion and the remainder initiator solution 1.5h, keep 79～81 ℃ of temperature of reaction, be added dropwise to complete back sustained reaction 1h.Be cooled to 30～50 ℃, regulate pH=7～9 dischargings with ammoniacal liquor.
Two, the preparation of organosilicon-modified acrylate finishing agent
Its composition and mass fraction are as follows:
45 parts of embodiment 4 emulsions
2.5 parts of BYK-348
0.5 part of Foamex815N
3 parts of HAS662
1 part of ammoniacal liquor
1.5 parts of card pines
46.5 parts of deionized waters;
Embodiment 4 emulsions are added in the stirring tank, add BYK-348, card pine, deionized water successively under continuing to stir, carry after stirring and add Foamex815N, HAS662, ammoniacal liquor more successively, the back discharging that continues to stir gets 100 parts of finishing agents.Gained finishing agent solid content is 15.8%, surface tension 28.5mN/m, viscosity 350mPas, pH value 7.9.
Embodiment 5
One, organosilicon-modified acrylate emulsion preparation
Employed concrete raw material and mass fraction proportioning are as follows:
55 parts of methyl methacrylates
28 parts of ethyl propenoates
4 parts of 2-Hydroxy ethyl acrylates
4 parts in vinylformic acid
2 parts of Vinylstyrenes
7 parts of vinyl silicone oils
3 parts in Nonyl pheno (10) ether
1.5 parts of sodium lauryl sulphate
0.8 part of ammonium persulphate
1.5 parts of sodium bicarbonates
400 parts of deionized waters
(1) preparation of stratum nucleare
Taking by weighing 1.5 parts of polyoxyethylene nonylphenol ethers, 0.75 part of sodium lauryl sulphate and 1.5 parts of sodium bicarbonates is dissolved in 200 parts of deionized waters and places reactor, under continue stirring, the mix monomer that 30 parts of methyl methacrylates, 14 parts of ethyl propenoates and 2 parts of 2-Hydroxy ethyl acrylates, 2 parts of vinylformic acid, 1 part of Vinylstyrene are formed adds in the reactor emulsification to forming stable emulsion and being warming up to 65～70 ℃.0.8 part of ammonium persulphate is dissolved in 130 parts of water and gets 50% its solution and add reactor and begin reaction, be warming up to 80 ℃ gradually, reaction 1.7h promptly gets the stratum nucleare emulsion, and control reaction temperature is 79～81 ℃ in the reaction process.
(2) preparation of organosilicon-modified acrylate emulsion
The remainder emulsifying agent is dissolved in the residue deionized water, adds whole vinyl silicone oils and remainder methyl methacrylate, ethyl propenoate, 2-Hydroxy ethyl acrylate, vinylformic acid, Vinylstyrene stirring and emulsifying to forming stable pre-emulsion.Continue reaction in the stratum nucleare emulsion with being added dropwise in this pre-emulsion and the remainder initiator solution 1.3h, keep 79～81 ℃ of temperature of reaction, be added dropwise to complete back sustained reaction 1h.Be cooled to 30～50 ℃, regulate pH=7～9 dischargings with ammoniacal liquor.
Two, the preparation of organosilicon-modified acrylate finishing agent
Its composition and mass fraction are as follows:
80 parts of embodiment 5 emulsions
3 parts of BYK-349
0.8 part of Foamex815N
3 parts of HAS662
1 part of ammoniacal liquor
1.5 parts of card pines
10.7 parts of deionized waters;
Embodiment 5 emulsions are added in the stirring tank, add BYK-349, card pine, deionized water successively under continuing to stir, carry after stirring and add Foamex815N, HAS662, ammoniacal liquor more successively, the back discharging that continues to stir gets 100 parts of finishing agents.Gained finishing agent solid content is 21.5%, surface tension 28.3mN/m, viscosity 300mPas, pH value 7.7.
Embodiment 6
One, organosilicon-modified acrylate emulsion preparation
Employed concrete raw material and mass fraction proportioning are as follows:
55 parts of methyl methacrylates
23 parts of ethyl propenoates
7 parts of butyl acrylates
4 parts of methacrylic acids-2-hydroxy methacrylate
4 parts of methacrylic acids
1 part of glycol ether diacrylate
6 parts of vinyltriethoxysilanes
2.5 parts in Nonyl pheno (10) ether
1.3 parts of sodium lauryl sulphate
0.8 part of ammonium persulphate
2 parts of sodium bicarbonates
230 parts of deionized waters
(1) preparation of stratum nucleare
Taking by weighing 1.38 parts of polyoxyethylene nonylphenol ethers, 0.72 part of sodium lauryl sulphate and 2 parts of sodium bicarbonates is dissolved in 100 parts of deionized waters and places reactor, under continue stirring, the mix monomer that 32 parts of methyl methacrylates, 14 parts of ethyl propenoates, 3.5 parts of butyl acrylates and 2 parts of methacrylic acid-2-hydroxy methacrylates, 3 parts of methacrylic acids, 0.5 part of glycol ether diacrylate are formed adds in the reactor emulsification to forming stable emulsion and being warming up to 65～70 ℃.0.8 part of ammonium persulphate is dissolved in 80 parts of water and gets 55% its solution and add reactor and begin reaction, be warming up to 80 ℃ gradually, reaction 1.8h promptly
Get the stratum nucleare emulsion, control reaction temperature is 79～81 ℃ in the reaction process.
(2) preparation of organosilicon-modified acrylate emulsion
The remainder emulsifying agent is dissolved in the residue deionized water, adds whole vinyltriethoxysilanes and remainder methyl methacrylate, ethyl propenoate, butyl acrylate, methacrylic acid-2-hydroxy methacrylate, methacrylic acid, glycol ether diacrylate stirring and emulsifying to forming stable pre-emulsion.Continue reaction in the stratum nucleare emulsion with being added dropwise in this pre-emulsion and the remainder initiator solution 1.2h, keep 79～81 ℃ of temperature of reaction, be added dropwise to complete back sustained reaction 1h.Be cooled to 30～50 ℃, regulate pH=7～9 dischargings with ammoniacal liquor.
Two, the preparation of organosilicon-modified acrylate finishing agent
Its composition and mass fraction are as follows:
50 parts of embodiment 6 emulsions
2.5 parts of WetKL245
0.5 part of Foamex815N
3 parts of HAS662
1 part of ammoniacal liquor
1 part of card pine
42 parts of deionized waters;
Embodiment 6 emulsions are added in the stirring tank, add Wet KL245, card pine, deionized water successively under continuing to stir, carry after stirring and add Foamex815N, HAS662, ammoniacal liquor more successively, the back discharging that continues to stir gets 100 parts of finishing agents.Gained finishing agent solid content is 19.5%, surface tension 28.5mN/m, viscosity 290mPas, pH value 7.7.
Embodiment 7
One, organosilicon-modified acrylate emulsion preparation
Employed concrete raw material and mass fraction proportioning are as follows:
60 parts of methyl methacrylates
25 parts of ethyl propenoates
4 parts in vinylformic acid-2-hydroxy propyl ester
4 parts in vinylformic acid
2 parts of methylene-bisacrylamides
5 parts of vinyl silicone oils
2.5 parts in Nonyl pheno (10) ether
1.3 parts of sodium lauryl sulphate
0.8 part of ammonium persulphate
1 part of sodium bicarbonate
230 parts of deionized waters
(1) preparation of stratum nucleare
Taking by weighing 1.3 parts of polyoxyethylene nonylphenol ethers, 0.7 part of sodium lauryl sulphate and 1 part of sodium bicarbonate is dissolved in 100 parts of deionized waters and places reactor, under continue stirring, with 31 parts of methyl methacrylates, 14 parts of ethyl propenoates, and the mix monomer formed of 2 parts of vinylformic acid-2-hydroxy propyl esters, 2 parts of vinylformic acid, 1 part of methylene-bisacrylamide add in the reactor emulsification to forming stable emulsion and being warming up to 65～70 ℃.0.8 part of ammonium persulphate is dissolved in 80 parts of water and gets 50% its solution and add reactor and begin reaction, be warming up to 80 ℃ gradually, reaction 1.7h promptly gets the stratum nucleare emulsion, and control reaction temperature is 79～81 ℃ in the reaction process.
(2) preparation of organosilicon-modified acrylate emulsion
The remainder emulsifying agent is dissolved in the residue deionized water, adds whole vinyl silicone oils and remainder methyl methacrylate, ethyl propenoate, vinylformic acid-2-hydroxy propyl ester, vinylformic acid, methylene-bisacrylamide stirring and emulsifying to forming stable pre-emulsion.Continue reaction in the stratum nucleare emulsion with being added dropwise in this pre-emulsion and the remainder initiator solution 1.3h, keep 79～81 ℃ of temperature of reaction, be added dropwise to complete back sustained reaction 1h.Be cooled to 30～50 ℃, regulate pH=7～9 dischargings with ammoniacal liquor.
Two, the preparation of organosilicon-modified acrylate finishing agent
Its composition and mass fraction are as follows:
60 parts of embodiment 7 emulsions
3 parts of Wet KL245
0.8 part of Foamex815N
3 parts of HAS662
1 part of ammoniacal liquor
1 part of card pine
31.2 parts of deionized waters;
Embodiment 7 emulsions are added in the stirring tank, add Wet KL245, card pine, deionized water successively under continuing to stir, carry after stirring and add Foamex815N, HAS662, ammoniacal liquor more successively, the back discharging that continues to stir gets 100 parts of finishing agents.Gained finishing agent solid content is 23%, surface tension 28mN/m, viscosity 320mPas, pH value 7.8.
With the finishing agent among the embodiment 1～7 and deionized water by dilution in 1: 19 after, handle disposable glove, the contrast of every performance of gained gloves and commercially available finishing agent is as shown in table 1, visible finishing agent of the present invention on every index all above the commercially available prod, alternative currently available products.
Table 1 gloves The performance test results
A kind of organosilicon-modified acrylate emulsion that the present invention proposes and being used to is made the preparation method of the finishing agent of powder-free gloves, be described by embodiment, person skilled obviously can be in not breaking away from content of the present invention, spirit and scope to prescription as herein described and method is changed or suitably change realize technology of the present invention with combination.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (8)
1. organosilicon-modified acrylate emulsion preparation method is characterized in that raw material is formed and mass fraction is as follows:
65～92 parts of acrylate
5～20 parts of function monomers
3～15 parts of organosilane monomers
1.5～7 parts of emulsifying agents
0.2～2 part of initiator
0.5～3 part of pH value buffer reagent
80～400 parts of deionized waters;
Its preparation method is as follows:
(1) preparation of stratum nucleare
Take by weighing that 40%～60% emulsifying agent and whole pH value buffer reagent are dissolved in 40%～50% deionized water and place reactor in the prescription, under continue stirring, the mix monomer that 40%～70% acrylate and 40%～70% function monomer are formed adds in the reactor emulsification to forming stable emulsion and being warming up to 65～70 ℃; Initiator is dissolved in 30%～40% deionized water and gets 40%～60% initiator solution and add reactor and begin reaction, be warming up to 75～85 ℃ gradually, reaction 1.5～2h promptly gets the stratum nucleare emulsion;
(2) preparation of organosilicon-modified acrylate emulsion
The remainder emulsifying agent is dissolved in the residue deionized water, adds whole organosilane monomers and remainder acrylate, function monomer stirring and emulsifying to forming stable pre-emulsion; Continue reaction in the stratum nucleare emulsion with being added dropwise in this pre-emulsion and the remainder initiator solution 1～1.5h, keep 75～85 ℃ of temperature of reaction, be added dropwise to complete back sustained reaction 1h; Be cooled to 30～50 ℃, regulate pH=7～9 dischargings with ammoniacal liquor;
Described function monomer is the mixture more than at least three kinds or three kinds in vinylformic acid, methacrylic acid, vinyl cyanide, 2-Hydroxy ethyl acrylate, vinylformic acid-2-hydroxy propyl ester, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester, glycol ether diacrylate, methylene-bisacrylamide or the Vinylstyrene;
Described organosilane monomer is that vinyltrimethoxy silane, vinyltriethoxysilane, vinyl methoxyl group diethoxy silane, gamma-methyl allyl acyloxypropyl trimethoxysilane or relative molecular mass are a kind of in 1000～2000 the vinyl silicone oil.
2. machine fluorine-silicon modified acrylic ester emulsion preparation method as claimed in claim 1 is characterized in that described acrylate is two or more the mixture at least in methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, Isooctyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate or the Isooctyl acrylate monomer.
3. machine fluorine-silicon modified acrylic ester emulsion preparation method as claimed in claim 1, it is characterized in that described emulsifying agent is the mixed emulsifier of nonionic emulsifying agent and anionic emulsifier collocation, the ratio of nonionic emulsifying agent and anionic emulsifier is between 1: 1～3: 1, nonionic emulsifying agent comprises alkylphenol polyoxyethylene or polyoxyethylene sorbitan fatty acid ester, and anionic emulsifier is sodium lauryl sulphate or Sodium dodecylbenzene sulfonate.
4. machine fluorine-silicon modified acrylic ester emulsion preparation method as claimed in claim 1 is characterized in that described initiator is ammonium persulphate, Sodium Persulfate or Potassium Persulphate; Described pH value buffer reagent is a sodium bicarbonate.
5. the machine fluorine-silicon modified acrylic ester emulsion of the described any machine fluorine-silicon modified acrylic ester emulsion preparation method preparation of claim 1～4 is used to make the preparation method of the finishing agent of powder-free gloves, it is characterized in that the composition of organosilicon-modified acrylate finishing agent and mass fraction are as follows:
40～80 parts of organosilicon-modified acrylate emulsions
0.5～5 part of base material wetting agent
0.05～1 part of defoamer
1～6 part of thickening material
0.1～3 part of pH value conditioning agent
0.5～3 part in sterilant
10～60 parts of deionized waters;
Organosilicon-modified acrylate emulsion is added in the stirring tank, continuing to add base material wetting agent, sterilant, deionized water successively under the stirring, add defoamer, thickening material, pH value conditioning agent after stirring again successively, the back discharging that continues to stir gets final product.
6. preparation method as claimed in claim 5 is characterized in that described base material wetting agent is the organic silicon modified by polyether class.
7. preparation method as claimed in claim 5 is characterized in that described defoamer is silicone based; Described thickening material is an association type alkali swelling class.
8. preparation method as claimed in claim 5 is characterized in that described pH value conditioning agent is a kind of in ammoniacal liquor, 2-amino-2-methyl-1-propanol, the quadrol; Described sterilant is the card pine.
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| TWI609640B (en) * | 2016-07-12 | 2018-01-01 | 帝藝國際貿易股份有限公司 | Composition for manufacturing gloves and method for manufacturing gloves by using composition |
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