CN104552688B - Curable fluorine resin demoulding agent and preparation method - Google Patents
Curable fluorine resin demoulding agent and preparation method Download PDFInfo
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Abstract
The invention discloses a curable fluorine resin demoulding agent and a preparation method. According to the curing fluorine resin demoulding agent, two fluorine resin copolymers of which the polymerization degree is not less than 500 are mixed; the fluorine resin copolymers are prepared by polymerizing vinylidene difluoride monomers and chlorotrifluoroethylene monomers. A curable low-toxicity fluorine resin demoulding agent composition with high film-forming property, high demoulding property and difficulty in gumming and thinning under a high temperature can be prepared under cooperation of organic solvents and a proper quantity of curing agents.
Description
Technical field
The present invention relates to a kind of curable fluororesin releasing agent is and in particular to a kind of hypotoxicity fluorine tree coordinating curing agent
Fat releasing agent and preparation method thereof.
Background technology
In polymeric material manufacture field, because releasing agent can prevent the products such as rubber, plastics to be bonded on mould, lead
Cause products appearance bad, the situation that qualification rate declines, and there is very important effect.But, the releasing agent such as talcum of early stage
Using inconvenience, the releasing agent such as vaseline, low molecular weight polyethylene, silicone oil is easy to remain the releasing agents such as powder, mica powder, soap
Oily face and affect the outward appearance of product, after the demoulding, product is difficult to directly to carry out secondary operation such as spray painting, printing, pastes etc.；Promote
Develop some new fluorine-containing demoulding agents in recent years, to solve the deficiency of early stage releasing agent.
The patent document of Patent No. CN103878910A discloses one kind with polytetrafluoroethylene (PTFE), stearic acid, carbon black and sulphur
Sulphur sodium, the rubber releasing agent of distilled water preparation.The patent document of Patent No. CN102782075A disclose a kind of by containing
Fluo-copolymer and the releasing agent of medium composition, this fluorinated copolymer contains the monomer based on the Polyfluoroalkyl with carbon number 1～6
The Component units of (a), the Component units of (methyl) acrylate (b) based on the alkyl with carbon number 18～30.Patent No.
The patent document of CN102596382A discloses poly- fluoroalkyl phosphonate emulsifying agent and taking off using this emulsifying agent as active ingredient
Mould agent.The patent document of Patent No. CN102458789A discloses a kind of graft copolymer and the demoulding with it as main component
Agent, this graft copolymer is to make formula CnF2n+1(CH2CF2)a(CF2CF2)bCH=CH2(wherein n is 1～6 integer, and a is 1
～4 integer, b is 1～3 integer) shown in how fluoro- 1-1 alkene carry out grafting altogether with PAG or its alkyl ether
Obtained by poly-.A kind of open novel noninflammability demoulding for mould of plastics of knowing clearly of the patent document of Patent No. CN1799805A
Agent composition, said composition comprises：(a) hydrofluoroether, (b) fluorocarbon oil, (c) fluorine based surfactant.Patent No. CN87102964A
Patent document disclose a kind of mold release compositions, including (a) at least perfluoroalkyl of a 4-20 carbon atom and 4-
The mixture of the perfluorinated alkenyl of 20 carbon atoms or polymer, and a kind of (b) ladder polymer of organic sesqui siloxane.Specially
The patent document for CN101186665A for the profit number disclose using vinylidene and trichlorine PVF mol ratio be 10～
30mol%：The monomer of 70～90mol% and organic peroxide carry out suspension polymerisation, obtain number-average molecular weight 5 ten thousand to 45 ten thousand
Fluororesin, and adopt ethanol, acetone equal solvent, the dispersant such as calcium carbonate, talcum powder and stearic acid dispersion aids make each
Plant corrosion resistant coating, direct construction usage can be passed through.
As described above, existing fluorine-containing demoulding agent needs particular monomers (as fluorinated acrylate, fluorine-containing alkyl phosphoric acid at present
Ester or phosphate) and be difficult to prepare containing fluorine graft copolymer, under thermoplastic fluorocarbon resin high temperature can gummosis thinning；Fluorine resin coating
Do not have solidification, under high temperature can gummosis it is difficult to meet the demand of demoulding during high-temperature molding；In such as polyurethanes and its derivative
Thing (concrete such as polyurethane plastics, polyurethane elastomer and foamed material), unsaturated polyester plastic, micro-nano slaine strengthen rubber
Have such problems as during the shaping such as moulding material that mould adhesion, the demoulding are difficult.
And, the present inventor finds under study for action, when polyurethane plastics and micro-nano slaine strengthen rubber-plastics material shaping
There is very strong stickness, be all difficult to obtain satisfaction using silicone releasing agent GMT457, MA2020 fluorine-containing demoulding agent etc.
High temperature release effect.
Content of the invention
[technical problem to be solved]
Present invention aim to address the problem that above-mentioned prior art exists, provide a kind of organic fluorine releasing agent, should
Releasing agent can be coated in die surface and dry solidification forms one layer of fluoropolymer material being difficult high temperature gummosis, and is to have
The hypotoxicity fluororesin releasing agent of good stripping result.
[technical scheme]
In order to reach above-mentioned technique effect, the present invention takes technical scheme below：
, by the degree of polymerization is not less than 500 two kinds of fluororesin copolymer mixing, this fluororesin copolymer is by inclined for the present invention
Fluoride monomers are polymerized with CTFE monomer；Under organic solvent, appropriate curing agent coordinate, it is obtained in that film forming
Property good, high temperature under be difficult the curable hypotoxicity fluororesin mold release compositions that gummosis is thinning, release property is good.
A kind of curable fluororesin releasing agent, it includes the component of following mass parts：
23 0.1～30 part of type organic fluorine mixtures；
70～99.9 parts of organic solvent；
0～5 part of curing agent；
Described 23 type organic fluorine mixtures be the material by vinylidene fluoride monomers Yu CTFE monomer amount it
Than for 1：The copolymer of (0.5～2) and vinylidene fluoride monomers are 1 with the ratio of the amount of the material of CTFE monomer：(2.2
～9) copolymer mixes.
In 23 type organic fluorine mixtures of the present invention, the amount of vinylidene fluoride monomers and CTFE monomeric substance
Ratio be 1：The content of the copolymer of (2.2～9) is 0～99%.
Organic solvent of the present invention is one or more organic solvent selected from ethers, lipid or halogenated hydrocarbon, ketone；
The toxicity of described organic solvent is not less than 2000mg/kg, boiling point between 50～170 DEG C for LD50.
Organic solvent of the present invention is to be selected from oxolane, methyl acetate, ethyl acetate, acetic acid third one or more
Ester, n-butyl acetate, sec-butyl acetate, tert-butyl acetate, pentyl acetate, butyl propionate, butyl butyrate, ethyl hexanoate, methyl
The organic solvent of methyl acrylate, EMA, chloroform, dioxane, acetone or cyclohexanone.
Curing agent of the present invention is the tri-alkoxy or dialkoxy silicane containing amino.
Curing agent of the present invention be one or more be selected from γ-aminopropyl-trialkoxy silane, N- (β-aminoethyl)-
γ-aminopropyl-trialkoxy silane, N- (β-aminoethyl)-γ-aminopropyltriethoxy dialkoxy silicane, γ-ureido-propyl-three
The consolidating of alkoxy silane, γ-(polyethylene amino) propyl trialkoxy silane or γ-amidino groups sulfopropyl trialkoxy silane
Agent；The alkoxyl of described curing agent is methoxy or ethoxy.
The preparation method of foregoing curable fluororesin releasing agent, it comprises the following steps：
A, the preparation of 23 type organic fluorine solution
23 type organic fluorine mixtures are dissolved in organic solvent, obtain 23 described type organic fluorine solution；
B, the mixing of curing agent
The 23 type organic fluorine solution that step A is obtained add curing agent, mix, and obtain described curable fluorine
Resin releasing agent.
The temperature of curing reaction of the present invention is 80～200 DEG C, and the time is no less than 30min.
Will be described in detail the present invention below.
A kind of curable fluororesin releasing agent, it includes the component of following mass parts：
23 0.1～30 part of type organic fluorine mixtures；
70～99.9 parts of organic solvent；
0～5 part of curing agent；
Described 23 type organic fluorine mixtures be the material by vinylidene fluoride monomers Yu CTFE monomer amount it
Than for 1：The copolymer of (0.5～2) and vinylidene fluoride monomers are 1 with the ratio of the amount of the material of CTFE monomer：(2.2
～9) copolymer mixes.
23 type organic fluorine mixtures of the present invention are the polymeric matrix material of fluororesin releasing agent, its polymerization
Monomer is vinylidene and CTFE, and its average composition is as shown in formula (I)：
(CH2CF2)n(CF2CFCl)m(I)
In average compositional formula (I), n, m represent vinylidene fluoride monomers and the degree of polymerization of CTFE monomer respectively,
It is respectively 1 in the n/m ratio of two kind of 23 type organic fluorine copolymer of the application：(0.5～2) and 1：(2.2～9).
23 type organic fluorine mixtures, can be using vinylidene fluoride monomers and CTFE monomer in normal temperature and pressurization bar
Obtained by free radical suspensioning polymerization under part.
The number-average degree of polymerization of 23 type organic fluorine mixtures of the present invention is n+m, is not less than 500, and is not more than
10000；
The number-average degree of polymerization preferably more than 1000, less than 5000 of 23 type organic fluorine mixtures of the present invention.
As long as the number-average degree of polymerization of 23 type organic fluorine mixtures is in the range of 500～10000,23 type organic fluorines
Mixture will have preferable dissolubility, mobility, good mechanical strength.
In the present invention 23 type organic fluorine mixture, the condition determination of molecular weight n or m of repetitive is to adopt the U.S.
Waters company produces M244 type ALC/GPC instrument, and mobile phase is ethyl acetate, and flow velocity is 1.0mL/min.
23 type organic fluorine n/m ratios of the present invention are 1：The copolymer of (0.5～2) scope, preferably n/m ratio is
1：1 or 1：2 copolymer；More preferably n/m ratio is 1：1 copolymer.
23 type organic fluorine n/m ratios of the present invention are 1：The copolymer of (2.2～9) scope, preferably n/m ratio is
(1：3)、(1：4) or (1：9) copolymer；More preferably 1：3 or 1：4 copolymer.
In 23 type organic fluorine mixtures of the present invention, the amount of vinylidene fluoride monomers and CTFE monomeric substance
Ratio be 1：The content of the copolymer of (2.2～9) is 0～99%.
In 23 type organic fluorine mixtures of the present invention, the amount of vinylidene fluoride monomers and CTFE monomeric substance
Ratio be 1：The content of the copolymer of (2.2～9) more preferably 30～70%.
As long as the n/m ratio of copolymer is respectively 1 in 23 type organic fluorine mixtures：(0.5～2) and 1：(2.2～
, and the ratio of content vinylidene fluoride monomers and the amount of CTFE monomeric substance is 1 9)：The content of the copolymer of (2.2～9)
During for 0～99%, this mixture will have preferable dissolubility, mobility, good mechanical strength, in high temperature film forming and
Mobility aspect keeps good effect.
23 type organic fluorine mixtures of the present invention to be calculated by 100 parts with the mass parts sum of organic solvent；Institute
State 23 type organic fluorine mixture preferably 0.1～30 mass parts, preferably 1～10 mass parts；Described 23 type organic fluorines mix
Compound more preferably 2～7 mass parts.Described organic solvent preferably 70～99.9 mass parts, preferably 90～99 mass parts, more preferably 93
～98 mass parts.As long as the mass parts of described 23 type organic fluorine mixtures and organic solvent are within this range, fluororesin takes off
The construction effect of mould agent just can obtain good guarantee.
Organic solvent of the present invention is one or more organic solvent selected from ethers, lipid or halogenated hydrocarbon, ketone；
The toxicity of described organic solvent is not less than 2000mg/kg, boiling point between 50～170 DEG C for LD50.
Organic solvent of the present invention is to be selected from oxolane, methyl acetate, ethyl acetate, acetic acid third one or more
Ester, n-butyl acetate, sec-butyl acetate, tert-butyl acetate, pentyl acetate, butyl propionate, butyl butyrate, ethyl hexanoate, methyl
The organic solvent of methyl acrylate, EMA, chloroform, dioxane, acetone or cyclohexanone.
The boiling point of organic solvent that the present invention uses and toxicity LD50 are as follows：
Oxolane (66 DEG C, 3000mg/kg), methyl acetate (57.8 DEG C, 5450mg/kg), ethyl acetate (77.1 DEG C,
5620mg/kg), propyl acetate (101 DEG C, 9370mg/kg), n-butyl acetate (126.5 DEG C, 13100mg/kg), acetic acid Zhong Ding
Ester (116 DEG C, 3200mg/kg), tert-butyl acetate (97.8 DEG C, 4100mg/kg), pentyl acetate (149.3 DEG C, 16600mg/
Kg), ethyl propionate (99.1 DEG C, 3500mg/kg), ethyl butyrate (121.3 DEG C, 13050mg/kg), butyl butyrate (166.6 DEG C,
9520mg/kg), ethyl hexanoate (168 DEG C, 5000mg/kg) and methyl methacrylate (101 DEG C, 7872mg/kg), methyl-prop
Olefin(e) acid ethyl ester (119 DEG C, 14800mg/kg), Isobutyl methacrylate (155 DEG C, 6400mg/kg), n-BMA
(163 DEG C, 12900mg/kg), chloroform (61.2 DEG C, 2180mg/kg), dioxane (101 DEG C, 6000mg/kg), acetone (56.5
DEG C, 9750mg/kg), cyclohexanone (155 DEG C, 3460mg/kg).
Organic solvent of the present invention is preferably LD50 and is not less than 3000mg/kg, and boiling point is in 60 DEG C～160 DEG C of ester
Class, ethers, halogenated hydrocarbon, one or more of organic solvent of ketone；More preferably LD50 is not less than 5000mg/kg, and boiling point is 60
DEG C～160 DEG C of ester, ether, halogenated hydrocarbons, one or more of the organic solvent of the micro- toxicity of ketone.Specifically, organic solvent is preferred
Oxolane, methyl acetate, ethyl acetate, acetic acid (just) butyl ester, pentyl acetate, acetone, one or more of ethyl butyrate.
The present invention does not have special restriction to the specification of organic solvent and purity, as long as after organic solvent volatilization no substantially
Residual, products surface quality and stripping result are no significantly affected, even technical grade, the pure organic solvent of chemistry
Can also.
As can be seen here, the material when present invention is all hypotoxic, and the fluororesin releasing agent preparing also is low toxicity
Property fluororesin releasing agent.
Curing agent of the present invention is the tri-alkoxy or dialkoxy silicane containing amino.
Curing agent of the present invention be one or more be selected from γ-aminopropyl-trialkoxy silane, N- (β-aminoethyl)-
γ-aminopropyl-trialkoxy silane, N- (β-aminoethyl)-γ-aminopropyltriethoxy dialkoxy silicane, γ-ureido-propyl-three
The consolidating of alkoxy silane, γ-(polyethylene amino) propyl trialkoxy silane or γ-amidino groups sulfopropyl trialkoxy silane
Agent；The alkoxyl of described curing agent is methoxy or ethoxy.
The alkoxyl of described curing agent is to ensure that the fluorine tree obtaining suitable stripping result for methoxy or ethoxy
Fat releasing agent.
Preferred γ-aminopropyl-the trialkoxy silane of curing agent of the present invention and/or N- (β-aminoethyl)-γ-ammonia third
Base-trialkoxy silane.
Hardener dose of the present invention is 0～5 mass parts；Preferably 0.01～3.0 mass parts；More preferably 0.2～1.0 matter
Amount part.
As long as the consumption of aminoalkoxysilane is in the range of 0～5 mass parts, just can obtain that solidification effect is good, have
The fluororesin releasing agent of good stripping result.That is, the present invention can add curing agent, use after fully crosslinked,
Curing agent can be added without use after releasing agent drying and forming-film.The fluororesin releasing agent of the present invention making after adding curing agent
With time or resting period, it is not particularly limited.
Fluororesin releasing agent of the present invention may also include levelling agent, thickener, anti-extension agent, dispersant, diluent, divides
Powder, emulsifying agent, one or more of water.
Levelling agent of the present invention such as moral is modest 466, EFKA3700, EFKA3770 etc..Such as YK-P104s, moral is modest for dispersant
D904S.Thickener such as SiO 2 powder.Levelling agent, thickener, anti-extension agent, the species of dispersant and consumption be not specific
Limit, be advisable with the using effect that disclosure satisfy that releasing agent.The species of emulsifying agent and consumption are existed with disclosure satisfy that fluorine-containing demoulding agent
In water, good emulsion dispersion, long-time stable are advisable.Special restriction, hydro carbons, ether are had no to diluent kind and specification, consumption
Class, halogenated hydrocarbon, esters, ketone, if boiling point in the range of 50～170 DEG C, LD50 in more than 2000mg/kg and
23 type fluororesin releasing agents mixing are significantly separated and incompatible situation occurs, the concentration of fluororesin keeps after dilution
More than 0.1%, disclosure satisfy that the use requirement of releasing agent.
The preparation method of foregoing curable fluororesin releasing agent, it comprises the following steps：
A, the preparation of 23 type organic fluorine solution
23 type organic fluorine mixtures are dissolved in organic solvent, obtain 23 described type organic fluorine solution；
23 type organic fluorine solution of the present invention are transparent, clarification solution.
B, the mixing of curing agent
The 23 type organic fluorine solution that step A is obtained add curing agent, mix, and obtain described curable fluorine
Resin releasing agent.
C, the application of fluororesin releasing agent
The curable fluororesin releasing agent that step B is obtained, coats the mold cavity surface of cleaning, drying, no rusty stain,
After its dry tack free, heat its surface so as to surface is fully cured.
In stepb, described mixing refers to gentle agitation so as to mix.
The temperature of curing reaction of the present invention is 80～200 DEG C, and the time is no less than 30min.
In the 23 type organic fluorine release agent solution preparation processes of the present invention, the concrete grammar of fluororesin dissolving is no clear and definite
Restriction, either long-time standing dissolving, stirring and dissolving or be heated to reflux dissolving etc. under room temperature.And the present invention is to room
The rotating speed of the time of the lower standing of temperature and addition temperature, stirring all no clearly limits, as long as its time, temperature and rotating speed reach 23
Type organic fluorine is completely dissolved.To time of the static dissolving of room temperature to be advisable no less than 2 days, preferably 3～20 days, more excellent
Select 7～14 days, as long as within this range, the dissolving of fluororesin is achieved with gratifying effect.
In stepb, curing agent can be added to use after fully crosslinked, also can be added without curing agent and be dried in releasing agent
Use after film.The fluororesin releasing agent of the present invention add curing agent after use time or the resting period, not special
Limit.
In step C, the solidification mode of heating of the fluororesin releasing agent of the present invention does not have special restriction.It is coated with the demoulding
The moulds of industrial equipment of agent, can may also be employed Far-infrared Heating, electric furnace heating wire heating, or even heat using air-conditioning constant temperature, baking oven heating
Metal plate heats.The solidification temperature of the fluororesin releasing agent of the present invention is advisable with 50 DEG C～250 DEG C, as long as releasing agent is in mould
Using at a temperature of temperature even more high not gummosis thinning.The solidification temperature condition of the fluororesin releasing agent of the present invention, preferably
140 DEG C ± 60 DEG C, as long as solidification temperature falls within the range so that it may obtain good crosslinking curing effect.
In step C, the hardening time of the fluororesin releasing agent of the present invention does not specifically limit, with fluororesin releasing agent
It is fully cured, gummosis or liquefaction are not advisable under high temperature.The hardening time condition of the fluororesin releasing agent of the present invention, preferably 140
Solidify at DEG C ± 60 DEG C and be advisable no less than 30min, as long as falling within the range so that it may obtain good cross-linking effect.
The material of the fluororesin releasing agent preparation of the present invention, even if also can smoothly obtain outward appearance under the conditions of pressurized, heated
The second best in quality product of rubber and plastic, is not required to pass through machining, you can obtain accurate size and good appearance again, exempts
Unnecessary operation.
The fluororesin releasing agent of the present invention, applies in rubber-plastics material shaping not only as releasing agent, also can be further
It is applied to the fields such as anti-corrosion material, coat, good protective action is played to various devices and material.
[beneficial effect]
The present invention compared with prior art, has following beneficial effect：
The material low toxicity that the present invention uses, simple and easy to get；It is thinning that the fluororesin releasing agent preparing is difficult high temperature gummosis.
And the fluororesin releasing agent stripping result of the present invention is good, products appearance quality good it may be unnecessary to extra machining, just
Accurate size and good appearance can be obtained.
According to the raw material of the present invention and its mass parts of use, no matter adopt the method such as organic solution or emulsion, all
The good organic fluorine releasing agent of release property can be obtained.
The releasing agent of the present invention is widely used, and also can further apply the fields such as anti-corrosion material, coat, to various devices
Part and material play good protective action.
Specific embodiment
With reference to embodiments of the invention, the invention will be further elaborated.Use a series of embodiments below
With comparative example, the present invention is specifically described, but the present invention is limited by following examples never in any form.Following
In embodiment, " part " refers to " mass parts ".
Embodiment 1：
First, by 3.5 number average molecular weights about 16 × 10423 type organic fluorine (CH2CF2)1(CF2CFCl)1(middle indigo plant
Morning twilight chemical research institute produces, trade mark F2311), with 3.5 number average molecular weights about 42 × 10423 type organic fluorines
(CH2CF2)1(CF2CFCl)4(Zhonglan Chenguang Chemical Inst produces, trade mark F2314) adds in sealable glass container, then
Add the oxolane (chemistry is pure) of 46.5 parts of butyl acetates (chemistry is pure) and 46.5 parts and seal up lid, in slight wobble stirring
Afterwards, place at room temperature, rock stirring once in 1～2d, treat that it naturally dissolves, becomes colourless or slightly yellow transparent solution.
Then, 0.2 part of KH550 coupling agent is added in fluororesin release agent solution, and rock stir, stand-by.
Finally, strengthen the mould of rubber-plastics material shaping for polyurethanes (foam) plastics or micro-nano carboxylic metallic salt
Tool mold cavity surface removes rusty stain, greasy dirt, and with absolute alcohol equal solvent cleaning, after surface is completely dried, is dipped with gauze
State fluorine-containing demoulding agent solution coating in mold cavity surface, after its dry tack free, heat its surface 60min at 140 DEG C, make
Its surface is fully cured film forming.
Molding mode according to polyurethanes (foam) plastics is molded and the demoulding using ready mould, according to
According to HB5479-91《The non-silicon mold release agent of composite》The effect that carries out of the stripping result method of inspection in aerospace industry standard is commented
Fixed.And the method according to micro-nano carboxylic metallic salt enhancing rubber-plastics material, carry out high temperature vulcanized crosslinking and stripping result grading, comment
Level standard is as follows：A- smooth in appearance, the demoulding is easy；B- smooth in appearance, sticking to mould area are less than the 5% of product surface, gently
Micro- sticking to mould, somewhat firmly can the smoothly demoulding；Rough complete, the sticking to mould area of C- outward appearance, more than the 10% of product surface, recruitment
Tool could the demoulding；D- product surface heavy damage, the demoulding is difficult.
Embodiment 2
First, 2.5 number F2311 are added in sealable glass container, be subsequently added into 97.5 parts of ethyl acetate, and seal
Upper lid, after slight wobble stirring, places at room temperature, rocks stirring once in 1～2d, treat that it naturally dissolves, becomes colourless
Or slightly yellow transparent solution.
Then, curing agent need not be added, similarly to Example 1 process mould, smearing release agent but be not required to carry out mould
Heat treatment；After releasing agent dry tack free, carry out the shaping of product of rubber and plastic, and the inspection of stripping result, grading evaluation.
Embodiment 3
First, by 10 parts of F2311, add in sealable glass container with 10 parts of F2314, be subsequently added into 40 parts of acetic acid fourths
The oxolane of ester and 40 parts simultaneously seals up lid, after slight wobble stirring, places at room temperature, rocks stirring one in 1～2d
Secondary, treat that it naturally dissolves, becomes colourless or slightly yellow transparent solution.
Then, 1.0 parts of KH550 coupling agent is added in fluororesin release agent solution, and rock stir, stand-by.
Finally, process mould, smearing release agent similarly to Example 1 and carry out die ＆ mold treatment；In releasing agent film forming
Afterwards, carry out the shaping of product of rubber and plastic, and the inspection of stripping result, grading evaluation.
Embodiment 4
First, 0.5 part of F2311 and 0.5 part of F2314 is added in sealable glass container, be subsequently added into 49.5 parts of second
The oxolane of acid butyl ester and 49.5 parts simultaneously seals up lid, after slight wobble stirring, places at room temperature, rocks in 1～2d and stir
Mix once, treat that it naturally dissolves, becomes colourless or slightly yellow transparent solution.
Then, 0.05 part of KH550 coupling agent is added in fluororesin release agent solution, and rock stir, stand-by.
Finally, process mould, smearing release agent similarly to Example 1 and carry out die ＆ mold treatment；On releasing agent surface
After drying and forming-film, carry out the shaping of product of rubber and plastic, and the inspection of stripping result, grading evaluation.
Comparative example 1
First, 0.02 part of F2311 and 0.02 part of F2314 is added in sealable glass container, be subsequently added into 40 parts of second
The oxolane of acid butyl ester and 49.96 parts simultaneously seals up lid, after slight wobble stirring, places at room temperature, rocks in 1～2d
Stirring once, treats that it naturally dissolves, becomes colourless or slightly yellow transparent solution.
Then, 0.05 part of KH550 coupling agent is added in fluororesin release agent solution, and rock stir, stand-by.
Finally, process mould, smearing release agent similarly to Example 1, carry out die ＆ mold treatment；Do on releasing agent surface
After dry, carry out the shaping of product of rubber and plastic, and the inspection of stripping result, grading evaluation.
Comparative example 2
First, 10 parts of F2311 and 10 part of F2314 are added in sealable glass container, be subsequently added into 40 parts of hexamethylenes
The oxolane of (80.7 DEG C of boiling point, LD50 value is 813mg/kg) and 40 parts simultaneously seals up lid, after slight wobble stirring, places
At room temperature, rock stirring once in 1～2d, treat that it naturally dissolves, becomes colourless or slightly yellow transparent solution.
Then, 6 parts of KH550 coupling agent is added in fluororesin release agent solution, and rock stir, stand-by.
Finally, process mould, smearing release agent similarly to Example 1, carry out die ＆ mold treatment；Do on releasing agent surface
After dry, carry out the shaping of product of rubber and plastic, and the inspection of stripping result, grading evaluation.
The stripping result inspection of each embodiment releasing agent of table 1, grading evaluation
From table 1, when organic solvent be added beyond 70～99.9 scope, obtained releasing agent stripping result
Difference, article outer surface are of poor quality；In addition, when curing agent adds excessive, also stripping result is poor for obtained releasing agent, outside product
Surface quality is poor.As can be seen here, only in appropriate organic solvent, the curing agent of arranging in pairs or groups, preferable releasing agent could be obtained.
Although reference be made herein to invention has been described for the explanatory embodiment of the present invention, and above-described embodiment is only this
Bright preferably embodiment, embodiments of the present invention are simultaneously not restricted to the described embodiments it should be appreciated that people in the art
Member can be designed that a lot of other modifications and embodiment, and these modifications and embodiment will fall in principle disclosed in the present application
Within scope and spirit.
Claims (6)
1. a kind of curable fluororesin releasing agent is it is characterised in that it includes the component of following mass parts：
23 0.1～30 part of type organic fluorine mixtures；
70～99.9 parts of organic solvent；
0～5 part of curing agent；
Described 23 type organic fluorine mixtures are that the ratio by vinylidene fluoride monomers and the amount of the material of CTFE monomer is
1：The copolymer of (0.5～2) and vinylidene fluoride monomers are 1 with the ratio of the amount of the material of CTFE monomer：(2.2～9)
Copolymer mix；
In described 23 type organic fluorine mixtures, vinylidene fluoride monomers are 1 with the ratio of the amount of CTFE monomeric substance：
The content of the copolymer of (2.2～9) is 0～99%；
Number-average degree of polymerization in described 23 type organic fluorine mixtures is not less than 500, and no more than 10000；
Described curing agent is the tri-alkoxy or dialkoxy silicane containing amino.
2. curable fluororesin releasing agent according to claim 1 is it is characterised in that described organic solvent is a kind of or many
Plant the organic solvent selected from ethers, lipid or halogenated hydrocarbon, ketone；The toxicity of described organic solvent is not less than for LD50
2000mg/kg, boiling point are between 50～170 DEG C.
3. curable fluororesin releasing agent according to claim 2 is it is characterised in that described organic solvent is a kind of or many
Plant and be selected from oxolane, methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, sec-butyl acetate, tert-butyl acetate, second
Sour pentyl ester, butyl propionate, butyl butyrate, ethyl hexanoate, methyl methacrylate, EMA, chloroform, dioxy six
The organic solvent of ring, acetone or cyclohexanone.
4. curable fluororesin releasing agent according to claim 1 is it is characterised in that described curing agent is one or more
Selected from γ-aminopropyl-trialkoxy silane, N- (β-aminoethyl)-γ-aminopropyl-trialkoxy silane, N- (β-aminoethyl)-
γ-aminopropyltriethoxy dialkoxy silicane, γ-ureido-propyl-trialkoxy silane, γ-(polyethylene amino) propyl group three alkane
TMOS or the curing agent of γ-amidino groups sulfopropyl trialkoxy silane；The alkoxyl of described curing agent is methoxyl group or second
Epoxide.
5. the curable fluororesin releasing agent according to Claims 1 to 4 any one preparation method it is characterised in that it
Comprise the following steps：
A, the preparation of 23 type organic fluorine solution
23 type organic fluorine mixtures are dissolved in organic solvent, obtain 23 described type organic fluorine solution；
B, the mixing of curing agent
The 23 type organic fluorine solution that step A is obtained add curing agent, mix, and obtain described curable fluororesin
Releasing agent.
6. the preparation method of fluororesin releasing agent according to claim 4 is it is characterised in that the temperature of described curing reaction
For 80～200 DEG C, the time is no less than 30min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0803337A2 (en) * | 1996-04-26 | 1997-10-29 | Hoechst Japan Limited | Release agent compositions |
| CN101659817A (en) * | 2009-10-12 | 2010-03-03 | 胡小林 | Fluoroelastomer coating with high fluorine content and low-temperature solidification |
| JP2012066447A (en) * | 2010-09-22 | 2012-04-05 | Shin Etsu Polymer Co Ltd | Mold release film |
| EP2537907A1 (en) * | 2010-02-15 | 2012-12-26 | Asahi Glass Company, Limited | Release agent composition |
| CN103878910A (en) * | 2014-04-14 | 2014-06-25 | 柳州市颖航汽配有限公司 | Rubber product demolding agent and preparation method thereof |
-
2015
- 2015-01-09 CN CN201510012665.9A patent/CN104552688B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0803337A2 (en) * | 1996-04-26 | 1997-10-29 | Hoechst Japan Limited | Release agent compositions |
| CN101659817A (en) * | 2009-10-12 | 2010-03-03 | 胡小林 | Fluoroelastomer coating with high fluorine content and low-temperature solidification |
| EP2537907A1 (en) * | 2010-02-15 | 2012-12-26 | Asahi Glass Company, Limited | Release agent composition |
| JP2012066447A (en) * | 2010-09-22 | 2012-04-05 | Shin Etsu Polymer Co Ltd | Mold release film |
| CN103878910A (en) * | 2014-04-14 | 2014-06-25 | 柳州市颖航汽配有限公司 | Rubber product demolding agent and preparation method thereof |
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