CN101338020B - Polymers resin for surface modification or adhesive joint of nonpolar plastic, preparation method and application thereof - Google Patents
Polymers resin for surface modification or adhesive joint of nonpolar plastic, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses polymer resin for the surface decoration or bonding of nonpolar plastic and a preparation method and an application thereof. The resin is comb structure polymer resin with hydroxyl at end groups or side groups, which contains hydrophobic long alkyl carbon chain side chains, and the hydroxyl content is 60 to 120 mgNaOH/g, the hydrophobic long alkyl carbon chain of the side chain of the resin is an alkane linear carbon chain with 10 to 12 carbon number; the main chain of the polymer is a carbon chain or a heterochain containing fat bases or a heterochain containing amine fat bases; the side chain and the main chain are connected by ester bond in a bonding mode. The polymer resin can be bonded and even entangled with polyolefin substrate by the long alkyl carbon chain having in the molecular chain, and can provide good adhesion for a coating layer. The ester bond and the amine ester bon both having in the molecule can provide a good mechanical performance for the resin. The polymer resin can be used in the coating agents or adhesives for the surfaces being not treated in polyolefine plastic products.
Description
Technical field
The present invention relates to a kind of resin and technology of preparing thereof, relate in particular to a kind of modification on non-polar plastic surface or fluoropolymer resin of bonding usefulness and its production and application of in filed of daily-use chemical industry, being used for.
Background technology
Polyolefin plastic products such as polyethylene, polypropylene, polyhutadiene, ethylene-propylene copolymer material have the performance of good physics and chemistry, owing to contain less polar material, the corrosion of the most of acid of ability, alkali in its molecular structure.Be insoluble to general solvent at normal temperatures, and because its linear structure and high crystalline energy, make resulting product have better plasticity, also has simultaneously impact-resistance preferably, therefore extensively be applied to preparing film, pipeline, various goods such as sheet material, thus occupy critical role in industries such as light packing, water supply and sewerage pipeline, household utensils, materials used in auto manufacturing.But also containing less polar material in the molecular structure just because of polyolefin plastics has caused this class material to have low polarity or nonpolar surface, cover with paint, lacquer, colour wash, etc. printing on to polyolefin plastic products or have certain difficulty when bonding in this apolar surfaces, because coating commonly used, printing ink and tackiness agent are more with the resin polar functionalities, polarity is bigger, the affinity of coating and printing ink therefore commonly used and tackiness agent and polyolefin plastics series base material is very poor, even all be difficult to wetting substrate surface, therefore the daily use to this material product has caused great restriction.
When handling this difficult problem, generally adopt two class methods at present both at home and abroad:
(1) polyolefine is carried out surface activation as the product of base material, this activation is in order to improve the surface energy of plastics, increase its surface tension, also promptly generate some polar groups or in addition alligatoring, so that coating is easier to be wetting and be adsorbed in the product surface at frosting.The method of surface activation process is a lot, as the chemical oxidation style, the flame oxidation method, solvent vapour etch method and corona discharge oxidation style, plasma method etc., practice is found, polyolefin substrate through surface activation process is enhanced on capillary raising and printing adaptability really, but, because the polyolefin substrate surface properties through surface activation process changes, lost and stablized inactive surface originally, and the method for surface active exists cost higher, bad to three-dimensional workpiece activation effect, the uneven defective of big area operation activation is so this class treatment process still can not solve whole issue.For this reason, a kind of surface-treated that do not carry out occurs and covered with paint, lacquer, colour wash, etc. mode of printing.
(2) use the chlorinatedpolyolefins mode and realize that treat surface is not covered with paint, lacquer, colour wash, etc. printing, the mode that chlorinatedpolyolefins is applied to not treat surface covering with paint printing mainly contains following several: (1) tackifier, be also referred to as adhesion promoter, in No. 6939916 patents of US, mention with chlorinatedpolyolefins or alkylene segmented copolymer, as the adhesion promoter coatings formulated, (as TPO) has good adhesivity to polyolefin substrate; (2) primary coat glue is mentioned with Chlorinated Polypropylene III and butadiene epoxy resin preparation primary coat glue in No. 7150107 patents of JP and to be applied to polyolefin substrate; (3) chlorinatedpolyolefins carries out being used for coating or printing ink after the graft modification, and the chlorine on the chlorinatedpolyolefins is obtained and can be covered with paint, lacquer, colour wash, etc. the resin material of printing not handling polyolefin surfaces by maleic anhydride or vinylformic acid reactive grafting.But, above-mentioned this class solution still has the defective of himself, because chlorinatedpolyolefins polarity is less, therefore as tackifier the time, be difficult to other component in coating or the printing ink, as pigment and other resins good compatibility is arranged, then brought the inconvenience of operation when using as primary coat glue, printing occasion in the disposable operation of needs is difficult to well be used, chlorinated polyolefin resin for graft modification generally can be applicable to more occasion, but this method is comparatively single to the monomer selectivity of graft reaction, thereby causes its mechanical property also more single.Thereby, because making, the existence of these defectives all can not be well solved not handling the problem of covering with paint, lacquer, colour wash, etc. printing on the polyolefin substrate always.
Summary of the invention
For solving the problems of the technologies described above, embodiment of the present invention provides a kind of non-polar plastic finishing or bonding with fluoropolymer resin and its production and application that is used for, adhere to, entwine by long alkane carbochain and the polyolefin substrate that has in the fluoropolymer resin molecular chain, for coat provides good sticking power, reach as being used in that cover with paint, lacquer, colour wash, etc. on the non-polar plastic surface or bonding effect.
The objective of the invention is to be achieved through the following technical solutions:
Embodiment of the present invention provides a kind of non-polar plastic finishing or bonding fluoropolymer resin of using of being used for, this resin is to contain hydrophobic long alkyl carbon chain side chain, end group to have the fluoropolymer resin that hydroxyl or side group have the comb-type structure of hydroxyl, its hydroxyl value content is 60～120mgNaOH/g, the hydrophobic long alkyl carbon chain of its side chain is that carbon atom quantity is 10～22 alkane line style carbochains, its main chain is carbochain or the heterochain that contains the fat base, or containing the heterochain of amine fat base, described side chain links to each other by the ester bond keyed jointing with described main chain;
The molecular structure expression formula of described fluoropolymer resin is any in following:
Molecular structure expression formula 1:
Wherein, A is:
N=9～21;
M is:---CH
2CH
2CH
2CH
2---,
Perhaps, the molecular structure expression formula 2:
Wherein, A is;
N=9～21;
B is: polyether glycol;
M is: tolylene diisocyanate, isophorone diisocyanate;
Perhaps, the molecular structure expression formula 3:
A
m——B
n——A
o——B
p(m+o)∶(n+p)＝1.7～2.4∶1，m+n+o+p＝3～450；
Wherein, A is:
N=9～21;
B is:
The molecular weight of described resin is 500～200000.
Embodiment of the present invention provides a kind of preparation method to each described resin in above-mentioned, and this method comprises:
Dihydroxylic and the reaction of the condensation polymerization between acid anhydrides, diprotic acid or binary isocyanic ester by the lipid acid Tegin 55G, or, prepare side chain and be long alkyl carbon chain, end group and have the fluoropolymer resin that hydroxyl or side group have the comb-type structure of hydroxyl by the free radical copolymerization between vinylformic acid higher alcohols ester compound and hydroxyl acrylic ester compound.
Embodiment of the present invention provides a kind of preparation method to each described resin in above-mentioned, and this method comprises:
Adopting following monomer is raw material: any in hexanodioic acid, the Tetra hydro Phthalic anhydride and glycerine monofatty ester combination, and wherein, the adipic-or phthalic acid acid anhydride: the lipid acid Tegin 55G is 1: 1.2～1.8 (mol ratios);
Use step-reaction polymerization, utilize the acid anhydrides or the diprotic acid dehydrating condensation polymerization at high temperature of two hydroxyls and the Tetra hydro Phthalic anhydride of glycerine monofatty ester, obtain having the fluoropolymer resin of hydrophobic group side chain and end group hydroxyl; Wherein, feed N during reaction
2Gas shield is warming up to 100 ℃ and is incubated all to melt to material and is liquid state, slowly is warming up to 160～180 ℃ again, and insulation reaction to water outlet is finished, vacuumize 1 hour after, survey acid number and reduce to the following cooling discharge of 5mgNaOH/g, promptly get resin product.
Described method also comprises: the output of products therefrom 〉=90%, hydroxy value measuring are 70～100mgNaOH/g.
Embodiment of the present invention provides a kind of preparation method to each described resin in above-mentioned, and this method comprises:
Adopting following monomer is raw material: any in tolylene diisocyanate, the isophorone diisocyanate and fatty acid monoglyceride and polyether glycol combination; Wherein, lipid acid Tegin 55G: tolylene diisocyanate or isophorone diisocyanate: polyether glycol is 1: 2.1～2.6: 2.2～2.8 (mol ratios);
Use step-reaction polymerization, glycerine monofatty ester is carried out polymerization with polyether glycol behind tolylene diisocyanate or isophorone diisocyanate end-blocking, obtain having the fluoropolymer resin of hydrophobic group side chain and end group hydroxyl; Wherein, feed N during reaction
2Gas shield is warming up to 80 ℃ of insulations three hours, adds polyether glycol and continues reaction 1～3 hour, promptly gets resin product.
Described method also comprises: the hydroxy value measuring of products therefrom is 80～100mgNaOH/g.
Embodiment of the present invention also provides a kind of preparation method to each described resin in above-mentioned, and this method comprises:
Adopting following monomer is raw material: vinylformic acid high-carbon alcohol ester and Hydroxyethyl acrylate combination, methylacrylic higher alcohols ester and Hydroxyethyl acrylate combination; Wherein, vinylformic acid high-carbon alcohol ester or methylacrylic higher alcohols ester: Hydroxyethyl acrylate is 1.7～2.4: 1 (mol ratio);
Adopt the arbitrary combination in the above-mentioned raw materials, carry out Raolical polymerizable, utilize the copolymerization and obtaining in the presence of initiator A IBN of vinylformic acid high-carbon alcohol ester or methylacrylic higher alcohols ester and vinylformic acid hydroxyl second fat to have hydrophobic group side chain and side group polymkeric substance for hydroxyl; Wherein, feed the N2 gas shield during reaction, be warming up to dimethylbenzene and return and heat up in a steamer three to five hours, cooling discharging also boils off dimethylbenzene, obtains resin product.
Embodiment of the present invention also provides a kind of preparation method to each described resin in above-mentioned, and this method comprises: with the mixture resin that obtains after the resin product blend for preparing in the claim 4,6 and 8.
Embodiment of the present invention also provide a kind of above-mentioned in each described resin application in coating or printing ink, this resin is used for the covering with paint protecting materials of non-polar polyolefinic surface of plastic products or polyethylene, polypropylene, polyhutadiene, ethylene-propylene copolymer material surface or adhesive coating or tackiness agent as the application that connects material or ancillary component in preparation.
The technical scheme that is provided by the invention described above embodiment as can be seen, the fluoropolymer resin of the embodiment of the invention is because its structure is the comb-shaped polymer with hydrophobic long side chain, its hydrophobic side chain is that carbon atom quantity is 10～22 alkane line style carbochains, the long side chain of this hydrophobic alkane can have good consistency with polyolefin substrate, also has certain crystallinity simultaneously, and because this side chain is to be connected on the main chain by ester bond, thereby it can solve the problem of the consistency of this resin and other material, the cohesive strength height of its resin own also has hydrocarbyl polymers and polyolefin articles excellent compatibility simultaneously.This fluoropolymer resin can adhere to by long alkane carbochain and the polyolefin substrate that has in the molecular chain, even entwine, can be for coat provide good sticking power, ester bond that has in the molecule and ammonia ester bond can provide the favorable mechanical performance for resin itself again.This fluoropolymer resin the not treat surface of polyolefin plastic products is covered with paint, lacquer, colour wash, etc. or bonding in, the pre-treatment that utilizes with respect to prior art, the processing mode of the original character of failure surface, as use chlorinatedpolyolefins as coating or bonding, the cohesive strength deficiency that causes, and performance is single, has extensively with the relatively poor grade of composition compatibility such as pigment and important use is worth.
Embodiment
Embodiment of the present invention provides a kind of non-polar plastic finishing or bonding with fluoropolymer resin and its production and application that is used for, this resin is to contain the fluoropolymer resin that hydrophobic long alkyl carbon chain side chain, end group or side group have the comb-type structure of hydroxyl, its hydroxyl value content is 60～120mgNaOH/g, the hydrophobic long alkyl carbon chain of its side chain is that carbon atom quantity is 10～22 alkane line style carbochains, its main chain is carbochain, contain the heterochain of fat base or contain the heterochain polymer of amine fat base, and described side chain links to each other by the ester bond keyed jointing with described main chain.The long side chain of hydrophobic alkane in this resin can have good consistency with polyolefin substrate, also has certain crystallinity simultaneously, and because this side chain is to be connected on the main chain by ester bond, thereby it can solve the problem of the consistency of this resin and other material.This resin can be applied to present some that widely applied and have low polarity or the polyolefin plastic products of apolar surfaces such as polyethylene; polypropylene; polyhutadiene; cover with paint, lacquer, colour wash, etc. the protection or the coating and printing ink and the adhesive material of bonding effect on the ethylene-propylene copolymer material surface, especially can be applicable to and cover with paint, lacquer, colour wash, etc. on the low polarity of not carrying out surface-active-treatment or the non-polar plastic goods in protection or the bonding coating and printing ink and tackiness agent.
For ease of understanding, further illustrate content of the present invention below by specific embodiment.
Embodiment one
Present embodiment provides a kind of fluoropolymer resin; can be applicable to and cover with paint, lacquer, colour wash, etc. on the low polarity of not carrying out surface-active-treatment or the non-polar plastic goods in the tackiness agent that protection or bonding coating or printing ink use; this resin is for containing hydrophobic long alkyl carbon chain side chain; end group or side group have the fluoropolymer resin of the comb-type structure of hydroxyl; its hydroxyl value content is 60～120mgNaOH/g; the hydrophobic long alkyl carbon chain of its side chain is that carbon atom quantity is 10～22 alkane line style carbochains; its main chain is a carbochain; the heterochain that contains the fat base; or containing the heterochain polymer of amine fat base, described side chain links to each other by the ester bond keyed jointing with described main chain.The unit that contains long alkyl carbon chain side chain in the molecular chain of this resin is that 10～22 line style alkanoic acid or alcohol obtain by the esterification with glycerine, acrylic or methacrylic acid by carbon atom quantity.The long side chain of this hydrophobic alkane can have good consistency with polyolefin substrate, also has certain crystallinity simultaneously, and because this side chain is to be connected on the main chain by ester bond, thereby it can solve the problem of the consistency of this resin and other material.The molecular weight of this fluoropolymer resin can be adjusted between 500～200000 according to reaction conditions.
Above-mentioned resin can be to react by the condensation polymerization between the dihydroxylic of lipid acid Tegin 55G and acid anhydrides, diprotic acid or binary isocyanic ester, or, prepare side chain and be long alkyl carbon chain, end group and have the fluoropolymer resin that hydroxyl or side group have the comb-type structure of hydroxyl by the free radical copolymerization between vinylformic acid higher alcohols ester compound and hydroxyl acrylic ester compound.
The molecular structure expression formula of this fluoropolymer resin can be any in following three kinds of forms:
First kind:
m＝1～10；
Wherein, A is:
N=9～21;
M is:---CH
2CH
2CH
2CH
2---,
Second kind:
m：0～5；
Wherein, A is;
N=9～21;
B is: polyether glycol;
M is: tolylene diisocyanate, isophorone diisocyanate;
The third:
A
m-B
n-A
o-B
p(m+o)∶(n+p)＝1.7～2.4∶1，m+n+o+p＝3～450；
Wherein, A is:
B is:
Above-mentioned fluoropolymer resin specifically can adopt following monomer to carry out polymerization and obtain, described monomer comprises: glycerine monofatty ester, vinylformic acid high-carbon alcohol ester, methylacrylic higher alcohols ester, Tetra hydro Phthalic anhydride, hexanodioic acid, polyether glycol, tolylene diisocyanate, isophorone diisocyanate etc.
Wherein, monomer component can obtain described fluoropolymer resin respectively by following polyreaction, specifically comprises:
(1) Tetra hydro Phthalic anhydride and lipid acid list grease carry out polycondensation;
(2) hexanodioic acid and glycerine monofatty ester carry out polycondensation;
In the reality, in (1), (2) item, each raw material consumption is: the adipic-or phthalic acid acid anhydride: the lipid acid Tegin 55G is 1: 1.2～1.8 (mol ratios);
(3) glycerine monofatty ester carries out polymerization with polyether glycol after toluene 2,4-are diisocyanate terminated;
(4) glycerine monofatty ester carries out polymerization with polyether glycol behind the isophorone diisocyanate end-blocking;
In the reality, in (3), (4) item, each raw material consumption is: the lipid acid Tegin 55G: tolylene diisocyanate or isophorone diisocyanate: polyether glycol is 1: 2.1～2.6: 2.2～2.8 (mol ratios);
(5) vinylformic acid high-carbon alcohol ester and vinylformic acid hydroxyl second fat carry out radical copolymerization;
(6) methylacrylic higher alcohols ester and vinylformic acid hydroxyl second fat carry out radical copolymerization.
In the reality, in (5), (6) item, each raw material consumption is: vinylformic acid high-carbon alcohol ester or methylacrylic higher alcohols ester: Hydroxyethyl acrylate is 1.7～2.4: 1 (mol ratio);
The fluoropolymer resin that obtains will be reacted in above-mentioned (1)-(6); after pressing the arbitrary proportion mixing; obtain a kind of fluoropolymer resin of mixed type, this hybrid resin also can be covered with paint, lacquer, colour wash, etc. on low polarity of not carrying out surface-active-treatment or non-polar plastic goods in protection or bonding coating and printing ink and the tackiness agent and use.The resin of this mixed type is different with the resin that adopts various monomer polymerization to obtain, and it can obtain a wider range and the hybrid resin of mechanical property excellence, thereby can solve the single problem of performance.
The comb polymers resin that present embodiment obtains is owing to have the long side chain of hydrophobic alkyl, thereby it is fine to the affinity of polyolefins plastics, this is to realize well attached primary basis, the present invention utilizes fatty acid ester, further again polymerization formed this comb-shaped polymer after vinylformic acid high-carbon ester reacted with corresponding polyfunctional compound, containing carbon chain lengths and be 10～22 fatty acid ester material has good amphipathic, being commonly used for surfactant in the daily-use chemical industry industry uses, therefore, the macromole with comb shaped structure of selecting for use phthalic anhydride or hexanodioic acid to carry out the polymerization gained with it not only has lipophilicity, and has mechanical property preferably.The end group of resulting polymers or side group have hydroxyl provides chemical reactivity functional group for its follow-up cure applications.
Above-mentioned fluoropolymer resin specifically is to make by the following method, comprise two kinds of progressively polymerization and radical polymerizations, wherein adopt Tetra hydro Phthalic anhydride respectively, hexanodioic acid, fatty acid mono glycidol, comb-shaped polymer that polyether glycol and polyisocyanates are polymerized uses is polymerization process progressively, is specially two hydroxyls utilizing glycerine monofatty ester and the acid anhydrides or the diprotic acid dehydrating condensation polymerization at high temperature of two functional groups; Perhaps utilize two hydroxyls of glycerine monofatty ester and tolylene diisocyanate or isophorone diisocyanate to carry out polyreaction, obtain having the product of isocyanate end with 1: 2 ratio, more further can with the polyether glycol polymerization with terminal hydroxy group.Then use the method for radical polymerization when adopting vinylformic acid high-carbon alcohol ester and methylacrylic higher alcohols ester to synthesize, be specially and utilize vinylformic acid high-carbon alcohol ester and methylacrylic higher alcohols ester in the presence of initiator A IBN, to obtain having the polymkeric substance of hydrophobic side chain with the Hydroxyethyl acrylate copolymerization.
Fluoropolymer resin of the present invention can use with solvent preparation becoming coating or printing ink commonly used, mainly is applicable to polyolefin plastic products is not being used on the treat surface.
Embodiment two
Present embodiment describes the process of preparation fluoropolymer resin, at first, gets each raw material:
Stearic acid monoglycerides (experiment level, Shanghai Ling Feng chemical reagents corporation)
Tetra hydro Phthalic anhydride (analytical pure, Tianjin Da Mao chemical reagents corporation)
Tosic acid (analytical pure, Tianjin Da Mao chemical reagents corporation)
Toluene (analytical pure, Tianjin Da Mao chemical reagents corporation)
Solidifying agent (employing polyisocyanate compound)
PE, PP film (marketing raw material)
With the 71g glyceryl monostearate, the 23g Tetra hydro Phthalic anhydride, the 0.3g tosic acid adds in the four-hole boiling flask, installs water trap, feeds N
2Gas shield is warming up to 100 ℃ and is incubated all to melt to material and is liquid state, slowly is warming up to about 160～180 ℃ again, and insulation reaction to water outlet is finished, and connects vacuum pump and vacuumizes, and begins to survey acid number after 1 hour, and acid number is reduced to and got final product cooling discharge below the 5mgNaOH/g.Products therefrom is shallow glassy yellow resin, and output is higher than 90%, and hydroxyl value is about 70～100mgNaOH/g after measured.
Performance for subsequent detection products therefrom resin, claim the 5g product to be made into toluene solution by the solid content of 35% solid content, press hydroxyl and isocyanic ester equimolar amount and add solidifying agent, it evenly is applied to the PE that cleaned through the acetone equal solvent, on the PP film, put into 80 ℃ of dryings of air dry oven 1 hour, and took out cooling back numbering and be respectively PE1 number, be used for test PP1 number.
Embodiment three
Present embodiment describes the process of preparation fluoropolymer resin, at first, gets each raw material:
Stearic acid monoglycerides (experiment level, Shanghai Ling Feng chemical reagents corporation)
Hexanodioic acid (analytical pure, Tianjin Da Mao chemical reagents corporation)
Tosic acid (analytical pure, Tianjin Da Mao chemical reagents corporation)
Toluene (analytical pure, Tianjin Da Mao chemical reagents corporation)
Solidifying agent (employing polyisocyanate compound)
PE, PP film (marketing raw material)
With the 71g glyceryl monostearate, the 21g Tetra hydro Phthalic anhydride, the 0.3g tosic acid adds in the four-hole boiling flask, installs water trap, feeds N
2Gas shield is warming up to 100 ℃ and is incubated all to melt to material and is liquid state, slowly is being warming up to about 160～180 ℃, and insulation reaction to water outlet is finished, and connects vacuum pump and vacuumizes, and begins to survey acid number after 1 hour, and acid number is reduced to and got final product cooling discharge below the 5mgNaOH/g.Products therefrom is shallow glassy yellow resin, and output is higher than 90%, and hydroxyl value is about 70～100mgNaOH/g after measured.
Performance for subsequent detection products therefrom resin, claim the 5g product to be made into toluene solution by 35% solid content, press hydroxyl and isocyanic ester equimolar amount and add solidifying agent, it evenly is applied to the PE that cleaned through the acetone equal solvent, on the PP film, put into 80 ℃ of dryings of air dry oven 1 hour, and took out cooling back numbering and be respectively PE2 number, be used for test PP2 number.
Embodiment four
Present embodiment describes the process of preparation fluoropolymer resin, at first, gets each raw material:
Lauric acid mono-glycerides (experiment level, Shanghai Ling Feng chemical reagents corporation)
Tetra hydro Phthalic anhydride (analytical pure, Tianjin Da Mao chemical reagents corporation)
Tosic acid (analytical pure, Tianjin Da Mao chemical reagents corporation)
Toluene (analytical pure, Tianjin Da Mao chemical reagents corporation)
Solidifying agent (employing polyisocyanate compound)
PE, PP film (marketing raw material)
With the 60g lauric monoglyceride, the 23g Tetra hydro Phthalic anhydride, the 0.3g tosic acid adds in the four-hole boiling flask, installs water trap, feeds N
2Gas shield is warming up to 100 ℃ and is incubated all to melt to material and is liquid state, slowly is being warming up to about 160～180 ℃, and insulation reaction to water outlet is finished, and connects vacuum pump and vacuumizes, and begins to survey acid number after 1 hour, and acid number is reduced to and got final product cooling discharge below the 5mgNaOH/g.Products therefrom is shallow glassy yellow resin, and output is higher than 90%, and hydroxyl value is about 70～1 00mgNaOH/g after measured.
Performance for subsequent detection products therefrom resin, claim the 5g product to be made into toluene solution by 35% solid content, press hydroxyl and isocyanic ester equimolar amount and add solidifying agent, it evenly is applied to the PE that cleaned through the acetone equal solvent, on the PP film, put into 80 ℃ of dryings of air dry oven 1 hour, and took out cooling back numbering and be respectively PE3 number, be used for test PP3 number.
Embodiment five
Present embodiment describes the process of preparation fluoropolymer resin, at first, gets each raw material:
Stearic acid monoglycerides (experiment level, Shanghai Ling Feng chemical reagents corporation)
Tolylene diisocyanate (analytical pure, Tianjin Da Mao chemical reagents corporation)
Polypropylene glycol 600 (marketing raw material)
Toluene (analytical pure, Tianjin Da Mao chemical reagents corporation)
Solidifying agent (employing polyisocyanate compound)
PE, PP film (marketing raw material)
With the 10g glyceryl monostearate, the 9.5g tolylene diisocyanate adds in the there-necked flask, feeds N
2Gas shield is warming up to 80 ℃ of insulations three hours, adds polypropylene glycol 10g and continues reaction 2 hours down at 80 ℃, and products therefrom is for having better mobile transparent resin, and hydroxyl value is about 80～100mgNaOH/g after measured.
Performance for subsequent detection products therefrom resin, claim the 5g product to be made into toluene solution by 35% solid content, press hydroxyl and isocyanic ester equimolar amount and add solidifying agent, it evenly is applied to the PE that cleaned through the acetone equal solvent, on the PP film, put into 80 ℃ of dryings of air dry oven 1 hour, and took out cooling back numbering and be respectively PE4 number, be used for test PP4 number.
Embodiment six
Present embodiment describes the process of preparation fluoropolymer resin, at first, gets each raw material:
Stearic acid monoglycerides (experiment level, Shanghai Ling Feng chemical reagents corporation)
Isophorone diisocyanate (analytical pure, Tianjin Da Mao chemical reagents corporation)
Cetomacrogol 1000 (marketing raw material)
Tosic acid (analytical pure, Tianjin Da Mao chemical reagents corporation)
Toluene (analytical pure, Tianjin Da Mao chemical reagents corporation)
Solidifying agent (employing polyisocyanate compound)
PE, PP film (marketing raw material)
With the 10g glyceryl monostearate, the 12g isophorone diisocyanate, 0.3% p-methyl benzenesulfonic acid adds in the there-necked flask, feeds N
2Gas shield is warming up to 80 ℃ of insulations three hours, adds polyoxyethylene glycol 10g, and products therefrom is for having better mobile transparent resin, and hydroxyl value is about 80～100mgNaOH/g after measured.
Performance for subsequent detection products therefrom resin, claim the 5g product to be made into toluene solution by 35% solid content, press hydroxyl and isocyanic ester equimolar amount and add solidifying agent, it evenly is applied to the PE that cleaned through the acetone equal solvent, on the PP film, put into 80 ℃ of dryings of air dry oven 1 hour, and took out cooling back numbering and be respectively PE5 number, be used for test PP5 number.
Embodiment seven
Present embodiment describes the process of preparation fluoropolymer resin, at first, gets each raw material:
Octadecyl acrylate (self-control)
Hydroxyethyl acrylate (analytical pure, Tianjin Da Mao chemical reagents corporation)
AIBN (catalyzer, Tianjin Da Mao chemical reagents corporation)
Dimethylbenzene (analytical pure, Tianjin Da Mao chemical reagents corporation)
Solidifying agent (employing polyisocyanate compound)
PE, PP film (marketing raw material)
With the 40g octadecyl acrylate, the 10g Hydroxyethyl acrylate, 20g dimethylbenzene, 3% initiator A IBN adds in the there-necked flask, feeds N
2Gas shield was warming up to refluxing xylene three to five hours, and cooling discharging also boils off dimethylbenzene, and products therefrom is for having better mobile transparent resin.
Performance for subsequent detection products therefrom resin, claim the 5g product to be made into toluene solution after measuring hydroxyl value by 35% solid content, press hydroxyl and isocyanic ester equimolar amount and add solidifying agent, it evenly is applied to the PE that cleaned through the acetone equal solvent, on the PP film, put into 80 ℃ of dryings of air dry oven 1 hour, and took out cooling back numbering and be respectively PE6 number, be used for test PP6 number.
Adopting vinylformic acid 18 fat in the present embodiment is a kind of in the vinylformic acid high-carbon alcohol ester, only illustrates as an example with vinylformic acid 18 fat, also can adopt vinylformic acid 16 fat or vinylformic acid 20 fat etc.
Embodiment eight
Present embodiment describes the process of preparation fluoropolymer resin, at first, gets each raw material:
Stearyl methacrylate (self-control)
Hydroxyethyl acrylate (analytical pure, Tianjin Da Mao chemical reagents corporation)
AIBN (catalyzer, Tianjin Da Mao chemical reagents corporation)
Toluene (analytical pure, Tianjin Da Mao chemical reagents corporation)
Solidifying agent (employing polyisocyanate compound)
PE, PP film (marketing raw material)
With the 40g stearyl methacrylate, the 10g Hydroxyethyl acrylate, 20g dimethylbenzene, 3% initiator A IBN adds in the there-necked flask, feeds N
2Gas shield was warming up to refluxing xylene three to five hours, and cooling discharging also boils off dimethylbenzene, and products therefrom is for having better mobile transparent resin.
Performance for subsequent detection products therefrom resin, claim the 5g product to be made into toluene solution after measuring hydroxyl value by 35% solid content, press hydroxyl and isocyanic ester equimolar amount and add solidifying agent, it evenly is applied to the PE that cleaned through the acetone equal solvent, on the PP film, put into air dry oven 80 ℃ dry 1 hour down, take out cooling back numbering and be respectively PE7 number, be used for test PP7 number.
Embodiment nine
Present embodiment mixed with embodiment two resulting polymers resins the foregoing description one with 1: 1, obtain the fluoropolymer resin of mixed type.
Performance for subsequent detection products therefrom resin, by 35% solid content the hybrid resin that obtains is made into toluene solution, press hydroxyl and isocyanic ester equimolar amount and add solidifying agent, it evenly is applied to the PE that cleaned through the acetone equal solvent, on the PP film, put into 80 ℃ of dryings of air dry oven 1 hour, and took out cooling back numbering and be respectively PE8, be used for test PP8 number.
To PE1-8 number that obtains among the foregoing description two～embodiment nine, the PP1-8 film sample is tested, and is specific as follows:
Test example 1: sticking power experiment
Test method: GB/T13217.7---91 attachment fastness method of inspection;
Test sample: among the embodiment PE1-8 of gained number, the PP1-8 film sample;
Assay: residual area 〉=85% that do not peel off;
According to detected result as can be known, the fluoropolymer resin of the embodiment of the invention to polyolefin articles not treat surface have adhesive ability preferably.
Test example 2: anti-solvent experiment
Test method: adopt drop-burette drippage alcohol solvent, drip and wear paint film solvent for use amount and be criterion;
Test sample: among the embodiment PE1-8 of gained number, the PP1-8 film sample;
Assay: drip quantity of solvent all greater than more than the 10mL, wherein 1,2, No. 3 polyester type better effects if of embodiment.
According to detected result as can be known, the fluoropolymer resin of the embodiment of the invention has solvent resistance preferably.
In sum; adopt the fluoropolymer resin of comb-type structure in the embodiment of the invention with hydrophobic long alkyl carbon chain side chain; solve the problem of the consistency of this resin and other material; can well have low polarity or the polyolefin plastic products of apolar surfaces such as polyethylene as some that widely applied at present; polypropylene; polyhutadiene is covered with paint, lacquer, colour wash, etc. the coating and printing ink and the adhesive material of protection or bonding effect on the ethylene-propylene copolymer material surface.
The above; only be the preferable embodiment of the present invention; but protection scope of the present invention is not limited thereto; the succession relation of each embodiment does not cause any restriction to the present invention yet; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (2)
1. one kind is used for non-polar plastic finishing or bonding preparation method with fluoropolymer resin, it is characterized in that this method comprises:
Prepare first fluoropolymer resin: adopting following monomer is raw material: any in hexanodioic acid, the Tetra hydro Phthalic anhydride and glycerine monofatty ester combination, and wherein, the adipic-or phthalic acid acid anhydride: the mol ratio of glycerine monofatty ester is 1: 1.2～1.8;
Use step-reaction polymerization, utilize the acid anhydrides or the diprotic acid dehydrating condensation polymerization at high temperature of two hydroxyls and the Tetra hydro Phthalic anhydride of glycerine monofatty ester, obtain having the fluoropolymer resin of hydrophobic group side chain and end group hydroxyl; Wherein, feed N during reaction
2Gas shield is warming up to 100 ℃ and is incubated all to melt to material and is liquid state, slowly is warming up to 160～180 ℃ again, and insulation reaction to water outlet is finished, vacuumize 1 hour after, survey acid number and reduce to the following cooling discharge of 5mgNaOH/g, promptly get resin product;
Prepare second fluoropolymer resin, adopting following monomer is raw material: any in tolylene diisocyanate, the isophorone diisocyanate and glycerine monofatty ester and polyether glycol combination; Wherein, glycerine monofatty ester: tolylene diisocyanate or isophorone diisocyanate: the mol ratio of polyether glycol is 1: 2.1～2.6: 2.2～2.8;
Use step-reaction polymerization, glycerine monofatty ester is carried out polymerization with polyether glycol behind tolylene diisocyanate or isophorone diisocyanate end-blocking, obtain having the fluoropolymer resin of hydrophobic group side chain and end group hydroxyl; Wherein, feed N during reaction
2Gas shield is warming up to 80 ℃ of insulations three hours, adds polyether glycol and continues reaction 1～3 hour, promptly gets resin product;
Prepare the terpolymer resin, adopting following monomer is raw material: vinylformic acid high-carbon alcohol ester and Hydroxyethyl acrylate combination, methylacrylic higher alcohols ester and Hydroxyethyl acrylate combination; Wherein, vinylformic acid high-carbon alcohol ester or methylacrylic higher alcohols ester: the mol ratio of Hydroxyethyl acrylate is 1.7～2.4: 1;
Adopt the arbitrary combination in the above-mentioned raw materials, carry out Raolical polymerizable, utilize the copolymerization and obtaining in the presence of initiator A IBN of vinylformic acid high-carbon alcohol ester or methylacrylic higher alcohols ester and Hydroxyethyl acrylate to have hydrophobic group side chain and side group polymkeric substance for hydroxyl; Wherein, feed N during reaction
2Gas shield is warming up to dimethylbenzene and returns and heat up in a steamer three to five hours, and cooling discharging also boils off dimethylbenzene, obtains resin product;
To prepare first fluoropolymer resin, preparation second fluoropolymer resin and prepare the mixture resin that obtains after the fluoropolymer resin product blend for preparing in the terpolymer resin;
First fluoropolymer resin of above-mentioned preparation, second fluoropolymer resin or terpolymer resin are and contain hydrophobic long alkyl carbon chain side chain, end group and have the fluoropolymer resin that hydroxyl or side group have the comb-type structure of hydroxyl, its hydroxyl value content is 60～120mgNaOH/g, the hydrophobic long alkyl carbon chain of its side chain is that carbon atom quantity is 10～22 alkane line style carbochains, its main chain is carbochain or the heterochain that contains ester group, or containing the heterochain of amine ester group, described side chain links to each other by the ester bond keyed jointing with described main chain;
The molecular structure expression formula of first fluoropolymer resin of described preparation, second fluoropolymer resin or terpolymer resin is any in following:
Molecular structure expression formula 1:
Wherein, A is:
M is:---CH
2CH
2CH
2CH
2-,
Perhaps, the molecular structure expression formula 2:
Wherein, A is;
B is: polyether glycol;
M is: tolylene diisocyanate, isophorone diisocyanate;
Perhaps, the molecular structure expression formula 3:
A
m-B
n-A
o-B
p(m+o)∶(n+p)＝1.7～2.4∶1，m+n+o+p＝3～450；
Wherein, A is:
B is:
2. non-polar plastic finishing or the bonding preparation method with fluoropolymer resin of being used for according to claim 1 is characterized in that the molecular weight of described fluoropolymer resin is 500～200000.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517380A (en) * | 2002-12-18 | 2004-08-04 | Composition for using polywax with biological absorptivity and medical device | |
| US20070264204A1 (en) * | 2006-05-11 | 2007-11-15 | Air Products And Chemicals, Inc. | Personal care compositions containing functionalized polymers |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517380A (en) * | 2002-12-18 | 2004-08-04 | Composition for using polywax with biological absorptivity and medical device | |
| US20070264204A1 (en) * | 2006-05-11 | 2007-11-15 | Air Products And Chemicals, Inc. | Personal care compositions containing functionalized polymers |
Non-Patent Citations (1)
| Title |
|---|
| 兰云军等.阴离子水性脂肪族聚氨酯复鞣填充剂的合成.《中国皮革》.2005,第34卷(第9期),1-5. * |
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