A kind of metachloroethylene copolymer latex of salt fog resistance
Technical field
The present invention relates to a kind of metachloroethylene copolymer latex, particularly relate to a kind of salt fog resistance vinylidene chloride,
The copolymer emulsion of vinyl chloride, acrylate and acrylamide.
Background technology
DOW chemical company of the U.S. in 1932 has started the research of vinylidene chloride polymerization, but vinylidene chloride homopolymer
Softening temperature is sufficiently close to decomposition temperature, and is crystalline polymer.Equal in order to improve vinylidene chloride
The softening temperature of polymers and degree of crystallinity, obtain being total to of classes such as vinyl-chloride-containing, acrylate, acrylonitrile in succession
Aggressiveness.In the fifties in last century, inclined chlorine copolymer resins and latex all have their application report, glue at that time
Newborn is mainly used for dip-coating paper and makees coating.
At present, vinylidene chloride copolymer latex coating has good wearability, moisture resistance, oil resistant, resistance to because of it
The excellent properties such as chemical drugs etch, barrier and anti-flammability, are widely used in packaging for foodstuff, automobile
The fields such as industry, the fire-retardant processing of fiber and concrete curing.But it is domestic to aqueous metachloroethylene copolymer glue
The research of breast is less, and the product of actual application has not been entered into market, mainly due to the emulsion-stabilizing after polymerization
Property bad, long-term place after the easiest breakdown of emulsion of emulsion, coalescence, the adhesive force of film, salt spray resistance reach not simultaneously
Index request to coating.
US3351991A discloses a kind of barrier based on metachloroethylene copolymer/heat sealability coating, the most partially
Vinyl chloride copolymer is formed by vinylidene chloride, acrylonitrile, methyl methacrylate and unsaturated fatty acid copolymerization.
This coating is used for crystalline polypropylene film coating, to improve the heat sealability of goods, moisture-proof and barrier.
US3736303A discloses a kind of latex based on metachloroethylene copolymer, this metachloroethylene copolymer by
The vinylidene chloride of 70-95%, the vinyl unsaturated sulfonic acid of 0.1-3.0%, the vinyl unsaturated carboxylic acid of 0-5%
Other unsaturated vinyl monomer copolymerization with 2-29.9% form.This latex paint is for painting polyethylene or poly-
Ethylene base material, modified by chemical copolymerization, to improve the adhesion under high humidity environment.
EP0261337A2 discloses a kind of terpolymer latex, this copolymer by 80-87.5% vinylidene chloride,
The methyl methacrylate of 7-14.5% and the acrylic acid copolymer of 4.5-6.5% form.This latex paint is used for being coated with
Polypropylene fibre, to improve barrier and the thermostability of goods.
CN101033276A discloses a kind of auto-deposition based on vinylidene chloride-acrylate copolymer latex and is coated with
Material and each method processed.With vinylidene chloride and acrylate as monomer, synthesize vinylidene chloride-acrylate copolymer
Latex, adds dispersible pigment color paste, hydrogen peroxide, iron powder, Fluohydric acid. and deionized water and is configured to autodeposition coatings,
Alternative electrophoretic paint, for the application of metal base, is also applied for body of a motor car, vehicle frame and smallclothes metal device
The application of part.
CN103059192A discloses a kind of polyvinylidene chloride copolymer latex for inner, external wall coating and system thereof
Method and application, this PVDC copolymer latex is by the mixing containing a certain amount of vinylidene chloride, vinyl chloride and acrylate
Monomer, auxiliary agent, initiator, emulsifying agent containing dodecylbenzene sodium sulfonate and OP-10 or OP-4 are through being once polymerized
Method prepares.This PVDC latex makes stable system, can place 24 months not breakdown of emulsion, nothings at 30 DEG C under RH70%
Precipitation, do not destroyed by calcium ions and magnesium ions during use, with its prepare inner, external wall coating have environmental protection, waterproof,
The features such as protection against the tide, anti-flammability.
Above patent has been directed to comonomer and has carried out modified polyvinilidene vinyl chloride, but latex still suffers from dehydrochlorination
Reaction, easily variable color, colour stability is bad, the easy variable color of thin film after coating, foaming, it is impossible to time long
Between keep clear, colorless state, prior art does not has can solve this problem well.
Summary of the invention
Not enough for prior art, the present invention provides a kind of with vinylidene chloride as main monomer, vinyl chloride, propylene
Acid esters and acrylamide monomer carry out the metachloroethylene copolymer latex of the salt fog resistance of modification by copolymerization.
To achieve the above object of the invention, the present invention can use any one technical scheme following:
One aspect of the present invention provide a kind of salt fog resistance metachloroethylene copolymer latex, described copolymer emulsion by
The raw material of following parts by weight is made by emulsion polymerization: mix monomer 100 parts, emulsifying agent 0.5-5 part, draw
Send out agent 0.05-0.5 part, pH adjusting agent 0.05-2 part, chain-transferring agent 0.05-0.2 part and deionized water 50-400
Part;
Described mix monomer consists of the following components in percentage by weight: vinylidene chloride 50-90%, vinyl chloride
5-30%, acrylic ester monomer 1-20% and acrylamide monomers 1-5%;
Described emulsifying agent is amphoteric emulsifier and/or nonionic emulsifier;
Described initiator is azo compound or persulfate;
Described pH adjusting agent is hydrophosphate or bicarbonate;
Described chain-transferring agent is aliphatic mercaptan;
The metachloroethylene copolymer latex of described salt fog resistance prepares as follows:
(1) in reactor, add deionized water and emulsifying agent, start stirring, use high pure nitrogen replacement
In system, residual air is less than 30ppm to oxygen content in still;
(2) add in still stir under Vinyl Chloride Monomer, part initiator and pH adjusting agent, room temperature pre-dispersed
20-30min;
(3) reactor is warming up to 40-80 DEG C, improves reactor speed of agitator, adds vinylidene chloride monomer and third
Olefin(e) acid esters monomer and residue initiator, keep reactor reaction pressure set polymerization pressure ±
0.01MPa;
(4) then drip acrylamide monomers, control reaction temperature 40-80 DEG C;
(5) when polymerization pressure declines 0.1-0.3MPa, add chain-transferring agent, stop stirring, reduce
Reaction temperature, residual gas in releasing reactor, discharging obtains metachloroethylene copolymer latex;
Described raw material is made up of the component of following weight portion: mix monomer 100 parts, emulsifying agent 1-3 part, initiation
Agent 0.1-0.3 part, pH adjusting agent 0.5-1 part, chain-transferring agent 0.08-0.15 part and deionized water 80-200 part;
Described acrylic ester monomer is selected from methacrylate, acrylic acid methyl ester., ethyl acrylate, propylene
Acid N-butyl and acrylic acid-2-ethyl caproite in one or more;
Described acrylic amide is selected from 2-acrylamide, 2-Methacrylamide, N hydroxymethyl acrylamide,
One or more in N, N-diethyl-2-acrylamide;
Described amphoteric emulsifier is selected from alkyl phenol polyethenoxy ether sodium sulfate salt;Nonionic emulsifier is selected from octyl group
Phenol polyethenoxy ether or NPE;
Described azo compound is 2,2 '-azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo two isopropylformic acid. two
Methyl ester or azo dicyclohexyl formonitrile HCN;Described persulfate is potassium peroxydisulfate, sodium peroxydisulfate or Ammonium persulfate.;
Described pH adjusting agent is disodium hydrogen phosphate, sodium dihydrogen phosphate or sodium bicarbonate;
Described chain-transferring agent is n-dodecyl mercaptan or n-octadecane base mercaptan.
Wherein, in the present invention as stated above, described part initiator is 0.1-0.4:1 with the weight ratio of residue initiator.
The present invention is by aggregation Monomer Formations, emulsifiers formula, polymeric reaction temperature and time, charging
Modes etc. affect the factor of polyreaction, optimize polymerization, are obtained by the preparation method of the present invention
Metachloroethylene copolymer latex due to polymerization in introduce vinyl chloride, unsaturated fatty acid and acrylamide monomer,
Make whole molecular structure can strengthen the flexibility of molecule segment, the property that resin is excellent can be given,
It is widely used in the fields such as packaging, automobile, food service industry, there is preferable market prospect.With prior art phase
Ratio, the method have the advantages that
1, copolymerization is carried out by vinylidene chloride, vinyl chloride, unsaturated fatty acid and four kinds of monomers of acrylamide,
Optimize the chain structure of main chain, improve the stability of latex, resistance to water and salt fog resistance;
2, by adjusting, improving emulsifier and coupling, improve the storage stability of latex, particle diameter is equal
Even, adhesion is strong;
3, by optimizing processing step, introduce different monomers at different polymerization stages, the most effectively control poly-
Close reaction rate, the composition of copolymer and the molecular weight of copolymer, form the inclined chloroethene that composition is relatively uniform
Alkene copolymer latex.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to this
A little detailed description of the invention.One skilled in the art would recognize that and present invention encompasses Claims scope
Interior potentially included all alternatives, improvement project and equivalents.
Embodiment 1
500g deionized water and emulsifying agent (10g OPEO is added in 2L reactor
(X-100)), starting stirring, in using high pure nitrogen displacement system, residual air is less than to oxygen content in still
30ppm;In still, add 90g Vinyl Chloride Monomer, 0.2g potassium peroxydisulfate and 3g sodium bicarbonate, stir under room temperature
Pre-dispersed 25min;Reactor is warming up to 60 DEG C, improves reactor speed of agitator, adds 347g vinylidene chloride list
Body and 50g acrylic acid-2-ethyl caproite base monomer and 0.8g potassium peroxydisulfate, keep reactor reaction pressure setting
Polymerization pressure ± 0.01MPa;Then dropping N hydroxymethyl acrylamide monomer 10g, controls reaction temperature
60℃;When polymerization pressure declines 0.2MPa, add n-dodecyl mercaptan 1g, stop stirring, fall
Low reaction temperatures, residual gas in releasing reactor, discharging obtains metachloroethylene copolymer latex.It is prepared into
The performance parameter of the vinylidene chloride copolymer latex arrived is as shown in table 1.
Embodiment 2
500g deionized water and (10g OPEO (X-100)) is added in 2L reactor,
Starting stirring, in using high pure nitrogen displacement system, residual air is less than 30ppm to oxygen content in still;In still
Add and stir pre-dispersed 25min under 90g Vinyl Chloride Monomer, 0.2g potassium peroxydisulfate and 3g sodium bicarbonate, room temperature;Instead
Answer still to be warming up to 60 DEG C, improve reactor speed of agitator, add 325g vinylidene chloride monomer and 76g acrylic acid-2-
Ethyl hexyl ester based monomer and 0.8g potassium peroxydisulfate, keep reactor reaction pressure setting polymerization pressure
±0.01MPa;Then dropping N hydroxymethyl acrylamide monomer 10g, controls reaction temperature 60 DEG C;When polymerization is anti-
When answering pressure to decline 0.2MPa, add n-dodecyl mercaptan 1g, stop stirring, reduce reaction temperature, release
Putting residual gas in reactor, discharging obtains metachloroethylene copolymer latex.The vinylidene chloride prepared is altogether
The performance parameter of agglomerating latex is as shown in table 1.
Embodiment 3
500g deionized water and emulsifying agent (10g OPEO is added in 2L reactor
(X-100)), starting stirring, in using high pure nitrogen displacement system, residual air is low to oxygen content in still
In 30ppm;90g Vinyl Chloride Monomer, 0.1g potassium peroxydisulfate and 3g sodium bicarbonate, room temperature is added in still
The lower pre-dispersed 25min of stirring;Reactor is warming up to 60 DEG C, improves reactor speed of agitator, adds 334g
Vinylidene chloride monomer and 50g acrylic acid-2-ethyl caproite base monomer and 0.9g potassium peroxydisulfate, keep reactor
Reaction pressure set polymerization pressure ± 0.01MPa;Then dropping N hydroxymethyl acrylamide monomer
24g, controls reaction temperature 60 DEG C;When polymerization pressure declines 0.2MPa, add dodecyl
Mercaptan 1g, stops stirring, reduces reaction temperature, and residual gas in releasing reactor, discharging obtains inclined chloroethene
Alkene copolymer latex.The performance parameter of the vinylidene chloride copolymer latex prepared is as shown in table 1.
Embodiment 4
500g deionized water and compound emulsifying agent ((5g OPEO is added in 2L reactor
(X-100) and 5g alkyl phenol polyethenoxy ether sodium sulfate salt (VA-50)), start stirring, use High Purity Nitrogen
In gas displacement system, residual air is less than 30ppm to oxygen content in still;In still add 90g Vinyl Chloride Monomer,
Pre-dispersed 25min is stirred under 0.2g potassium peroxydisulfate and 3g sodium bicarbonate, room temperature;Reactor is warming up to 60 DEG C, carries
High reactor speed of agitator, add 347g vinylidene chloride monomer and 50g acrylic acid-2-ethyl caproite base monomer and
0.8g potassium peroxydisulfate, keep reactor reaction pressure set polymerization pressure ± 0.01MPa;Then drip
Add N hydroxymethyl acrylamide monomer 10g, control reaction temperature 60 DEG C;When polymerization pressure declines 0.2MPa
Time, add n-dodecyl mercaptan 1g, stop stirring, reduce residue gas in reaction temperature, releasing reactor
Body, discharging obtains metachloroethylene copolymer latex.The performance parameter of the vinylidene chloride copolymer latex prepared
As shown in table 1.
Comparative example 1
500g deionized water and emulsifying agent (10g OPEO is added in 2L reactor
(X-100)), starting stirring, in using high pure nitrogen displacement system, residual air is low to oxygen content in still
In 30ppm;90g Vinyl Chloride Monomer, 0.1g potassium peroxydisulfate and 3g sodium bicarbonate, room temperature is added in still
The lower pre-dispersed 25min of stirring;Reactor is warming up to 60 DEG C, improves reactor speed of agitator, adds 360g
Vinylidene chloride monomer and 50g acrylic acid-2-ethyl caproite base monomer and 0.9g potassium peroxydisulfate, keep reactor
Reaction pressure set polymerization pressure ± 0.01MPa, control reaction temperature 60 DEG C;Work as polyreaction
When pressure declines 0.2MPa, add n-dodecyl mercaptan 1g, stop stirring, reduce reaction temperature, release
Putting residual gas in reactor, discharging obtains metachloroethylene copolymer latex.The vinylidene chloride prepared is altogether
The performance parameter of agglomerating latex is as shown in table 1.
Comparative example 2
500g deionized water and emulsifying agent (10g OPEO is added in 2L reactor
(X-100)), starting stirring, in using high pure nitrogen displacement system, residual air is low to oxygen content in still
In 30ppm;90g Vinyl Chloride Monomer, 0.1g potassium peroxydisulfate and 3g sodium bicarbonate, room temperature is added in still
The lower pre-dispersed 25min of stirring;Reactor is warming up to 60 DEG C, improves reactor speed of agitator, adds 385g
Vinylidene chloride monomer and 0.9g potassium peroxydisulfate, keep reactor reaction pressure setting polymerization pressure
±0.01MPa;Then dropping N hydroxymethyl acrylamide monomer 24g, controls reaction temperature 60 DEG C;When poly-
When closing reaction pressure decline 0.2MPa, add n-dodecyl mercaptan 1g, stop stirring, reduce and react temperature
Degree, residual gas in releasing reactor, discharging obtains metachloroethylene copolymer latex.The inclined chlorine prepared
The performance parameter of ethylene copolymer latex is as shown in table 1.
Table 1: embodiment 1-4 and the physical index contrast comparing vinylidene chloride latex prepared by 1-2
Knowable to table 1 data, the present invention introduces unsaturated fatty acid and acrylamide two on main polymer chain
Kind of monomer carries out copolymerization, and have employed emulsifiers formula and the polymerization technique of optimization, have adjusted the chain group of main chain
Become and structure, improve surface tension and the viscosity of latex, improve the stability of latex.
Embodiment 5
The latex spreader that embodiment 1-4 and comparative example 1-2 prepare is coated uniformly on through degreasing and rust removal
On iron plate, coating thickness is emulsion thick about 120 μm, and film forming after 60 DEG C of baking and curing 30min, according to state
Family's its hardness of standard test (GB/T 6739-1996), adhesive force (GB/T 1720-1979), resistance to water
And salt fog resistance (GB/T 1771-91) (GB1733-93).
Table 2: vinylidene chloride latex coating performance prepared by embodiment 1-5 compares
Knowable to table 2 data, the present invention introduces unsaturated fatty acid and acrylamide two on main polymer chain
Kind of monomer carries out copolymerization, and have employed emulsifiers formula and the polymerization technique of optimization, and the latex prepared has
Standby excellent film performance, improves resistance to water and salt fog resistance.