CN101974115A - Preparation method for low-molecular weight polymer with yellowing resistance - Google Patents
Preparation method for low-molecular weight polymer with yellowing resistance Download PDFInfo
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- CN101974115A CN101974115A CN 201010519974 CN201010519974A CN101974115A CN 101974115 A CN101974115 A CN 101974115A CN 201010519974 CN201010519974 CN 201010519974 CN 201010519974 A CN201010519974 A CN 201010519974A CN 101974115 A CN101974115 A CN 101974115A
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Abstract
The invention belongs to the technical field of polymer synthesis, in particular to a preparation method for a low-molecular weight polymer with yellowing resistance. The polymerization reaction is carried out at certain temperature; the polymerization reaction is caused by the thermal decomposition of a radical initiator without using chain transfer agents, such as lauryl mercaptan and the like, and the degree of polymerization of the polymer is controlled only through regulating the polymerization conditions in the polymerization process. The molecular weight of the polymer can be controlled between 2500 and 14000. The preparation method is simple and has good repeatability. The prepared polymer has proper molecular weight distribution and good yellowing resistance.
Description
Technical field
The invention belongs to the polymkeric substance synthesis technical field, be specifically related to a kind of preparation method of low-molecular weight polymer.
Background technology
Polymkeric substance as acrylate resin, is to be obtained through addition polymerization by acrylate monomer, and characteristics are that main chain is a carbon carbon bond.Because carbon-carbon skeletal chain is stable, does not have unstable structure in the molecule, such polymkeric substance has excellent light, heat and chemical stability, acrylate resin usually is used to weathering resistance for this reason, the occasion that stain resistance, acid-fast alkali-proof etc. are had relatively high expectations is such as automobile finish, external wall lacquer etc.It is generally acknowledged that the existence of ester group makes acrylate be difficult to crystallization in the polymer lateral chain, by selecting different ester groups can realize the dissolving of acrylate in various different solvents and miscible with other resins, thereby acrylate resin not only has excellent weather resistance and also possesses extraordinary workability simultaneously.
Outstanding weather resistance and optical property make acrylate resin paint extensively at car surface and are praised highly, thereby the functional group that introduces in the resin makes resin can be cross-linked into physics and chemical property that reticulated structure has further improved coating under certain condition.Acrylate resin usually uses with solution state, at first is coated in bodywork surface in use, realizes that by ultraviolet (UV) or high temperature coating curing is crosslinked, however inevitably in this process solvent can constantly evaporate in the air.The volatilization of organic gas obviously is disadvantageous, not only impairs operator's health, more is unfavorable for environmental protection and has increased the danger of blast simultaneously, moreover also be a big obstacle to reducing cost.Reduce the organic inclusion of VOC(volatility for this reason) imperative.
Reduce VOC, must improve the solid content of fluoropolymer resin, had a variety of methods available at present, as the second-order transition temperature that reduces polymkeric substance in the acrylate resin, the molecular weight that reduces polymkeric substance etc.Can effectively reduce the organic inclusion of VOC(volatility though reduce the second-order transition temperature of resin), be unfavorable for like this guaranteeing that crosslinked back coating at room temperature has higher hardness, finally cause bad anti-machinability and scratch resistance.Reduce molecular weight and reducing the organic inclusion of VOC(volatility) aspect very effective, at present the method for reduction molecular weight commonly used is exactly to realize control to molecular weight by adding chain-transfer agents such as mercaptan, though success reached intended purposes, also brought significant side effects.Since the introducing of chain-transfer agent, the tangible influence that the stability of polymeric matrix can be subjected to, and anti-yellowing property descends greatly.Under such background, synthetic a kind of low molecular weight propylene acid ester resin with excellent anti-yellowing property is a problem that is sought after solving.
Summary of the invention
The objective of the invention is to propose a kind of preparation method with lower molecular weight coating polymer of anti-yellowing property.
The preparation method of the low-molecular weight polymer with anti-yellowing property that the present invention proposes is at certain temperature (60-200
oC) carry out under, preparation process is simple, good reproducibility, and the molecular weight of polymkeric substance can control effectively by the adjusting of simple temperature, initiator selection and monomer dropping speed simultaneously.This anti-xanthochromic low-molecular weight polymer matrix can be that homopolymer also can be a multipolymer.By copolymerization, can be so that be with functional group on the polymer molecular chain, these functional groups are selected from hydroxyl, acetoacetoxy groups, carboxyl, epoxy group(ing), a kind of in primary amino and the secondary amino group, or wherein several; The low-molecular weight polymer that the present invention proposes, number-average molecular weight is about 2500-14000; Molecular weight distribution is about 1.5-2.5; Above-mentioned multipolymer is polymerized at a certain temperature by monomer mixture, and described monomer comprises one or more non-functional acrylate or other monomers, one or more functionalized acrylate or other monomers.
The preparation that the present invention proposes has the method for the low-molecular weight polymer of anti-yellowing property, and concrete steps are as follows: at normal pressure, 60～200
oUnder the C reflection temperature, in the solvent medium of 1～1000 weight part, slowly drip 1～5000 weight parts monomers and 0.01～500 weight part initiator, 0.5～10 hour dropping time; Restock drips 0.01-500 weight part initiator subsequently, and constant temperature 0.1-5 hour, discharging promptly obtained the low-molecular weight polymer matrix.
Among the present invention, the reflection temperature is 60～200
oC, preferred 80～1500
oC.Solvent medium is 1～1000 weight part, preferred 50～600 weight parts.The monomer that drips is 1～5000 weight part, preferred 5～2000 weight parts; The initiator that drips is 0.01～500 weight part for the first time, preferred 5～100 weight parts; 0.5～10 hour dropping time, preferred 1～5 hour.Replenishing and dripping initiator is 0.01～500 weight part, preferred 1～100 weight part.
Among the present invention, used monomer is to pass through or do not pass through the industrial-grade monomer of purifying.Used solvent medium is a Benzyl Chloride, ethanol, toluene, dimethylbenzene, ethylbenzene, tetrahydrofuran (THF), ethyl acetate, isophorone, acetone, Virahol, trichloromethane, normal heptane, Cardura E10, Solvesso100, Solvesso150, a kind of among the Solvesso200, or wherein several combinations.
Used radical initiator is a dibenzoyl peroxide, azo-bis-isobutyl cyanide, azo two cyanogen in different heptan, the diperoxy dibenzoyl, benzoyl peroxide, tertbutyl peroxide, t-amyl peroxy hydrogen, ditertiary butyl peroxide, two t-amyl peroxy things, peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester, peroxidation trimethylacetic acid tert-pentyl ester, 1,1-di-tert-butyl peroxide-3,3, the 5-trimethyl-cyclohexane, 1, the 1-cyclohexane di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-tert-butyl peroxide hexane, 4, a kind of in 4-two (tert-butyl hydroperoxide) n-butyl pentanoate, or wherein several combinations.
Used monomer is selected from the functionalized monomer that methyl methacrylate (MMA), methyl acrylate (MA), vinylbenzene (St), methacrylic acid (MA) etc. contain carboxyl, hydroxyl acrylic hydroxyl ethyl ester (HEMA) etc. contains the functionalized monomer of hydroxyl, glycidyl methacrylate (GMA) etc. contains the functionalized monomer of epoxide group, methacrylic acid amino ethyl ester (AEMA) etc. contains among the amino functionalized monomer a kind of, or wherein several.
The method for preparing low-molecular weight polymer of the present invention can be used to prepare homopolymer or multipolymer; Can on molecular chain, introduce hydroxyl by copolymerization, acetoacetoxy groups, carboxyl, epoxy group(ing), a kind of in the functional groups such as primary amino and secondary amino group, or wherein several, be convenient to follow-up crosslinking reaction.
The low-molecular weight polymer matrix of preparation mainly reduces molecular weight by adding potent chain-transfer agent such as Dodecyl Mercaptan at present.Though aforesaid method can effectively reduce molecular weight, the anti-yellowing property of the polymkeric substance that obtains can descend greatly, is surpassing 100
oPlacing 1 hour polymeric matrix under the condition of C will obviously turn to be yellow.Comparatively speaking, the present invention has following characteristics: (1) process is simple, good reproducibility.(2) polymericular weight that obtains is controlled.(3) do not use chain-transfer agent.(4) polymkeric substance has good yellowing resistance.(5) low-molecular weight polymer that obtains can be that homopolymer also can be a multipolymer, and the introducing of comonomer simultaneously can obviously not change the molecular weight of product.
Description of drawings
Fig. 1 is embodiment result.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1
To disposing condenser, magnetic agitation adds 50 parts of toluene solvants in the flask of heating unit, and logical nitrogen purged 30 minutes under normal pressure, was heated to 80
oC slowly added 100 parts of monomers methyl methacrylate (MMA) in 1 hour.When adding monomer mixture, add the toluene solution of 2,2'-Azobis(2,4-dimethylvaleronitrile) (AVBN), comprise 10 parts of 10 parts of 2,2'-Azobis(2,4-dimethylvaleronitrile) (AVBN) and toluene.Temperature remains at 80 in the reaction
oC when monomer dropping finishes, adds 10 parts of initiator solutions once more after 30 minutes, comprise 10 parts of 10 parts of 2,2'-Azobis(2,4-dimethylvaleronitrile) (AVBN) and toluene, constant temperature discharging after 2 hours.
The polymkeric substance that obtains is measured through GPC, and Mn is 8390, and Mw is 17115, and the molecular weight distribution width is 2.04.
Embodiment 2
To disposing condenser, magnetic agitation adds 35 parts of xylene solvents and 15 parts of isophorones in the flask of heating unit, and logical nitrogen purged 30 minutes under normal pressure, was heated to 110
oC slowly added 100 parts of monomer initiator mixtures (MMA/HEMA 80/20) in 1 hour.When adding monomer mixture, add the xylene solution of tertbutyl peroxide, 10 parts (temperature remains at 110 in the reaction with dimethylbenzene to comprise 12 parts of tertbutyl peroxides
oC when monomer dropping finishes, adds 10 parts of initiator solutions once more after 30 minutes, comprise 10 parts of 10 parts of tertbutyl peroxides and dimethylbenzene, constant temperature discharging after 2 hours.
The polymkeric substance that obtains is measured through GPC, and Mn is 2930, and Mw is 5655, and the molecular weight distribution Tile Width is 1.93.
Embodiment 3
To disposing condenser, magnetic agitation adds 35 parts of toluene solvants and 15 parts of Cardura E10 in the flask of heating unit, and logical nitrogen purged 30 minutes under normal pressure, was heated to 80
oC slowly added 100 parts of monomers methyl methacrylate (MMA) in 4 hours.When adding monomer mixture, add the benzoyl peroxide tert-butyl ester and azo-bis-isobutyl cyanide toluene solution, comprise 8 parts of the benzoyl peroxide tert-butyl esters, 10 parts of 4 parts of azo-bis-isobutyl cyanides and toluene.Temperature remains at 80 in the reaction
oC when monomer dropping finishes, adds 10 parts of initiator solutions once more after 30 minutes, comprise 8 parts of the benzoyl peroxide tert-butyl esters, 10 parts of 4 parts of azo-bis-isobutyl cyanides and toluene, constant temperature discharging after 2 hours.
The polymkeric substance that obtains is measured through GPC, and Mn is 5640, and Mw is 12300, and the molecular weight distribution width is 2.18.
Embodiment 4
To disposing condenser, magnetic agitation adds 50 parts of xylene solvents in the flask of heating unit, and logical nitrogen purged 30 minutes under normal pressure, was heated to 110
oC slowly added 100 parts of monomers methyl methacrylate (MMA) in 1 hour.When adding monomer mixture, add the xylene solution of the peroxidation trimethylacetic acid tert-butyl ester, comprise 10 parts of 11 parts of the peroxidation trimethylacetic acid tert-butyl esters and dimethylbenzene.Temperature remains at 110 in the reaction
oC when monomer dropping finishes, adds 10 parts of initiator solutions once more after 30 minutes, comprise 10 parts of 11 parts of the peroxidation trimethylacetic acid tert-butyl esters and dimethylbenzene, constant temperature discharging after 2 hours.
The polymkeric substance that obtains is measured through GPC, and Mn is 3350, and Mw is 6400, and the molecular weight distribution width is 1.91.
Embodiment 5
To disposing condenser, magnetic agitation adds 30 parts of xylene solvents and 20 parts of Solvesso100 in the flask of heating unit, and logical nitrogen purged 30 minutes under normal pressure, was heated to 140
oC slowly added 100 parts of monomers methyl methacrylate (MMA/HEMA/BA 75/20/5) in 1 hour.When adding monomer mixture, add the xylene solution of t-amyl peroxy hydrogen, comprise 10 parts of 6 parts of t-amyl peroxy hydrogen and dimethylbenzene.Temperature remains at 140 in the reaction
oC when monomer dropping finishes, adds 10 parts of initiator solutions once more after 30 minutes, comprise 10 parts of 10 parts of t-amyl peroxy hydrogen and dimethylbenzene, constant temperature discharging after 2 hours.
The polymkeric substance that obtains is measured through GPC, and Mn is 2410, and Mw is 4554, and the molecular weight distribution width is 1.89.
Embodiment result: use model as the gel chromatography of HP1010 the polymkeric substance that obtains to be carried out molecular weight determination, selected GPC gel column model is Phenogel GPC 100KA, and its molecular weight detection scope is: 100～10,000,000.Use refractive index detector, moving phase is selected THF.The results are shown in shown in Figure 1.
Claims (6)
1. the preparation method with low-molecular weight polymer of anti-yellowing property is characterized in that concrete steps are as follows: at normal pressure, 60～200
oUnder the C reflection temperature, in the solvent medium of 1～1000 weight part, slowly drip 1～5000 weight parts monomers and 0.01～500 weight part initiator, 0.5～10 hour dropping time; Restock drips 0.01-500 weight part initiator subsequently, and constant temperature 0.1-5 hour, discharging promptly obtained required low-molecular weight polymer matrix; The number-average molecular weight of this polymkeric substance is 2500-14000; Molecular weight distribution is 1.5-2.5.
2. preparation method according to claim 1, it is characterized in that described solvent medium is a kind of among Benzyl Chloride, ethanol, toluene, dimethylbenzene, ethylbenzene, tetrahydrofuran (THF), ethyl acetate, isophorone, acetone, Virahol, trichloromethane, normal heptane, Cardura E10, Solvesso100, Solvesso150, the Solvesso200, or wherein several combinations.
3. preparation method according to claim 2, it is characterized in that described initiator is a dibenzoyl peroxide, azo-bis-isobutyl cyanide, azo two cyanogen in different heptan, the diperoxy dibenzoyl, benzoyl peroxide, tertbutyl peroxide, t-amyl peroxy hydrogen, ditertiary butyl peroxide, two t-amyl peroxy things, peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester, peroxidation trimethylacetic acid tert-pentyl ester, 1,1-di-tert-butyl peroxide-3,3, the 5-trimethyl-cyclohexane, 1, the 1-cyclohexane di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-tert-butyl peroxide hexane, 4, a kind of in 4-two (tert-butyl hydroperoxide) n-butyl pentanoate, or wherein several combinations.
4. preparation method according to claim 3 is characterized in that described monomer is functionalized monomer, the functionalized monomer of containing epoxide group of containing hydroxyl, contains among the amino functionalized monomer one or more.
5. preparation method according to claim 4 is characterized in that described monomer is one or more in methyl methacrylate, methyl acrylate, vinylbenzene, methacrylic acid, hydroxyl acrylic hydroxyl ethyl ester, glycidyl methacrylate, the methacrylic acid amino ethyl ester.
6. preparation method according to claim 4, it is characterized in that by copolymerization, make and be with functional group on the polymer molecular chain, these functional groups are selected from a kind of in hydroxyl, acetoacetoxy groups, carboxyl, epoxy group(ing), primary amino and the secondary amino group, or wherein several.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438253A (en) * | 2003-03-06 | 2003-08-27 | 华南理工大学 | Acrylate micro-emulsion with high solid content, its preparation method and use |
| CN101602858A (en) * | 2009-07-17 | 2009-12-16 | 中国海洋石油总公司 | A kind of water soluble acrylic acid epoxy resin and preparation method thereof |
| CN101613434A (en) * | 2009-07-15 | 2009-12-30 | 华南理工大学 | A kind of alcohol soluble polyacrylate resin and preparation method thereof and application |
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2010
- 2010-10-26 CN CN 201010519974 patent/CN101974115A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438253A (en) * | 2003-03-06 | 2003-08-27 | 华南理工大学 | Acrylate micro-emulsion with high solid content, its preparation method and use |
| CN101613434A (en) * | 2009-07-15 | 2009-12-30 | 华南理工大学 | A kind of alcohol soluble polyacrylate resin and preparation method thereof and application |
| CN101602858A (en) * | 2009-07-17 | 2009-12-16 | 中国海洋石油总公司 | A kind of water soluble acrylic acid epoxy resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《浙江大学硕士学位论文》 20030617 刘欣 St/AA/MMA树脂的合成及结构调控 第26页、37－40页 1－6 , 2 * |
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Application publication date: 20110216 |