CN103265672B - A kind of preparation method with the plant oil based toughner of nucleocapsid structure - Google Patents
A kind of preparation method with the plant oil based toughner of nucleocapsid structure Download PDFInfo
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- CN103265672B CN103265672B CN201310190288.9A CN201310190288A CN103265672B CN 103265672 B CN103265672 B CN 103265672B CN 201310190288 A CN201310190288 A CN 201310190288A CN 103265672 B CN103265672 B CN 103265672B
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Abstract
There is a preparation method for the plant oil based toughner of nucleocapsid structure, be characterized in using liquid vegetable oil as kernel, and it is appropriately crosslinked to adopt kernel to carry out, obtained metastable vegetables oil inner core.And then be polymerized one deck by the outside surface that grafting radical polymerization is combined in vegetables oil kernel and there is high workability and with polyvinyl chloride (PVC), there is the rigid polymer shell of close solubility parameter.By designing different nucleocapsid ratio, obtain the plant oil based nucleocapsid structure toughner being applicable to PVC.Gained plant oil based nucleocapsid structure toughner has cheap, the advantage such as toughening efficiency is high, environmental protection compared with traditional toughner (as acrylate copolymer ACR, chlorinatedpolyethylene CPE), and this type of plant oil based toughner with nucleocapsid structure can be widely used in the fields such as PVC building doors and windows section bar, tubing, pipe fitting, electric wire, penetration pipe, small household appliances.
Description
Technical field
The present invention relates to a kind of preparation method with the plant oil based toughner of nucleocapsid structure, belong to the preparation and modification field of functional high molecule material.
Background technology
Polyvinyl chloride (PVC) is one of four large commodity polymer materials, is also the macromolecular material of non-petroleum base route rare in numerous polymer.Because PVC produces primarily of calcium carbide route, depend on petroleum resources hardly.The price of the mechanical property of its excellence, self-extinguishing and relative moderate has made it have a wide range of applications in fields such as toy, footwear industry, building, decoration, agriculturals.At present, the global output of PVC has broken through 4,000 ten thousand tons/year.Wherein, there is the manufacture being used to PVC material of construction more than 50% respectively, also just mean that the annual usage quantity of PVC toughner will more than 1,500,000 tons.
ACR is the most widely used analog assistant in current PVC field, is also a kind of esters of acrylic acid nano material with nucleocapsid structure simultaneously, its current average market valency Yue Wei $2 ten thousand/ton.Plasticizing promotor (or plasticizing conditioning agent) and toughner two kinds can be divided into according to the difference of nanoparticle core shell volume ratio.Wherein, when the content of polymethylmethacrylate (PMMA) shell is relatively less, and stratum nucleare is called toughner when being the rubber such as lightly crosslinked butyl polyacrylate or polyhutadiene, this type of ACR toughner can increase substantially the shock resistance of material under the condition reducing PVC material intensity and rigidity hardly.Because rigidity PMMA has the solubility parameter close with PVC, excellent compatibility between the two on the one hand; On the other hand, in nanoparticle, the existence of stratum nucleare soft rubber phase can make material by the deformation of rubber, impact energy be dissipated when being subject to foreign impacts, thus reaches the object of anti-impact.But regrettably to directly results in its final product price high for the preparation method of ACR complexity and technique, and market acceptance is limited.
Chlorinatedpolyethylene (CPE) is the class network-type toughner that current domestic PVC field is most widely used, and it obtains mainly through powdery polyethylene direct chlorination.There is toughness reinforcing excellent property, lower-price characteristic.But the production process of CPE will produce a large amount of acid-bearing wastewater, the aftertreatment problem of this type of waste water will be the stubborn problem the most that relevant enterprise faces always.Therefore, although the production technique of CPE is relatively simple, the energy consumption obtaining product is high, seriously polluted, does not possess sustainable developability.
Plant main body of oil is Unsaturatcd fatty acid glycerides, wherein containing the primitive (unsaturated double-bond) in a large number with reactive behavior, so carry out copolymerization by suitable method to it.As industrial under polybutadiene rubber existent condition, by the same to the graft polymerization production high impact polystyrene (HIPS) of its remaining unsaturated double-bond.
For the above-mentioned defect of traditional toughner such as ACR, CPE, and in conjunction with the chemical structure feature of vegetables oil, if can adopt and ACR molecular structure and the similar method of space structure design, and manage to obtain to there is the vegetables oil of environmental protection and Sustainable development feature for kernel by molecular designing, and adopt the material of polymkeric substance as shell with PVC macromolecular chain with superior compatibility, then can obtain there is nucleocapsid structure and the novel PVC toughner of toughness reinforcing excellent property.
Summary of the invention
The object of the invention is a kind of preparation method with the plant oil based toughner of nucleocapsid structure proposed for prior art deficiency, be characterized in using appropriately crosslinked liquid vegetable oil as kernel, the outside surface being then combined in vegetables oil kernel by grafting radical polymerization is polymerized the rigid polymer shell that one deck and PVC have close solubility parameter.By designing different nucleocapsid ratio, obtain the plant oil based nucleocapsid structure toughner being applicable to PVC material of construction.
Object of the present invention has following technical measures to realize, and wherein raw-material number is mass fraction except specified otherwise.
There is the preparation method of the plant oil based toughner of nucleocapsid structure:
1. there is a preparation method for the plant oil based toughner of nucleocapsid structure, it is characterized in that the method comprises the following steps:
(1) initiator A consumption be 0 ~ 5% quality than under condition, with emulsifying agent, assistant for emulsifying agent and dispersion agent, liquid vegetable oil is carried out emulsification, obtains the vegetables oil emulsion of particle size range at 10 ~ 400nm;
(2) adopt linking agent to carry out appropriately crosslinked to emulsified vegetable oil, it is 0 ~ 5% mass ratio that degree of crosslinking controls;
(3) mix by liquid vegetable oil, high workability monomer and the close solubility parameter monomer weight ratio of PVC 5 ~ 100:5 ~ 25:5 ~ 100, and be polymerized 1 ~ 8 hour at temperature 0 ~ 90 DEG C and initiator B consumption 0 ~ 15% condition, the plant oil based toughner of nucleocapsid structure must be had;
2., according to the preparation method described in claim 1 with the plant oil based toughner of nucleocapsid structure, it is characterized in that initiator A is at least one in peroxy dicarbonate, hydrogen peroxide, Potassium Persulphate, ammonium persulphate; Initiator B is at least one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dicumyl peroxide, peroxy dicarbonate, hydrogen peroxide, Potassium Persulphate, ammonium persulphate;
3., according to the preparation method described in claim 1 with the plant oil based toughner of nucleocapsid structure, it is characterized in that emulsifying agent is at least one in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, alkylphenol polyoxyethylene, tween, class of department, alkyl, polyether, sorbeth; Assistant for emulsifying agent is at least one in Virahol, propyl carbinol, the trimethyl carbinol, octanol, enanthol, lauryl alcohol;
4., according to the preparation method described in claim 1 with the plant oil based toughner of nucleocapsid structure, it is characterized in that dispersion agent is at least one in polyvinyl alcohol, methylcellulose gum, hydroxypropylcellulose, HPMC, carboxy cellulose, carboxy cellulose sodium, sodium alginate, gelatin, calcium carbonate, magnesiumcarbonate, talcum powder;
5., according to the preparation method described in claim 1 with the plant oil based toughner of nucleocapsid structure, it is characterized in that liquid vegetable oil is at least one in soybean oil, rapeseed oil, Semen Maydis oil, peanut oil, sesame oil, sunflower seed oil, Oleum Gossypii semen, sweet oil, plam oil, Viscotrol C;
6., according to the preparation method described in claim 1 with the plant oil based toughner of nucleocapsid structure, it is characterized in that linking agent is at least one of Vinylstyrene, diene acrylate, maleic anhydride;
7., according to the preparation method described in claim 1 with the plant oil based toughner of nucleocapsid structure, it is characterized in that high workability monomer is at least one in vinylbenzene, Vinylstyrene, methyl methacrylate, vinyl cyanide;
8., according to the preparation method described in claim 1 with the plant oil based toughner of nucleocapsid structure, it is characterized in that the close solubility parameter monomer of PVC is at least one in methyl acrylate, ethyl propenoate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, vinylchlorid, Ethylene Dichloride, vinylidene chloride, vinyl acetate;
9. according to the plant oil based toughner with nucleocapsid structure that method described in claim 1 obtains;
10. according to described in claim 12 for the plant oil based toughner with nucleocapsid structure in PVC building doors and windows section bar, tubing, pipe fitting, electric wire, penetration pipe, small household appliances field.
The advantage that the present invention has:
1. this invention exploits a kind of plant oil based toughner with nucleocapsid structure;
2. the plant oil based toughner with nucleocapsid structure prepared by the present invention has that toughening efficiency is high, consumption is few, the feature excellent with PVC consistency;
3. the plant oil based toughner with nucleocapsid structure prepared by the present invention can replace traditional toughner ACR and CPE, remarkable in economical benefits completely.
Accompanying drawing explanation
Fig. 1 has the chemical structure schematic diagram of the plant oil based toughner of nucleocapsid structure.
The mechanical property of the plant oil based toughner matrix material of Fig. 2 PVC/.
Specific embodiment
Below by specific embodiment, the present invention is specifically described; what be necessary to herein means out is that the present embodiment is only for the invention will be further described; can not be interpreted as limiting the scope of the invention, the those of skill in the art in this field can make improvement and the adjustment of some unsubstantialities to the present invention according to the content of foregoing invention.
Embodiment 1
100g deionized water, 6g alkyl, polyether Emulsion of soybean oil agent, 3g Sodium dodecylbenzene sulfonate, 0.1g polyvinyl alcohol, 1g Potassium Persulphate and 100g liquid soy oil is added successively in the four-hole boiling flask carrying heating and whipping appts.High-speed stirring 10 minutes under normal temperature, obtains soybean oil emulsion.In above-mentioned soybean oil emulsion, add 5g Vinylstyrene under agitation condition, raise temperature of reaction system to 75 DEG C, insulation reaction is cooled to normal temperature and namely obtains toughner kernel emulsion after 4 hours simultaneously.
In above-mentioned toughner kernel emulsion, add 5g Potassium Persulphate, 10g vinylbenzene and 100g methyl methacrylate successively, after high-speed stirring is even, gradually system temperature is increased to 75 DEG C, system temperature was increased to 82 DEG C after 3 hours by insulation reaction further.System is cooled to normal temperature and namely obtains the soybean oil based toughner with nucleocapsid structure by continuation insulation reaction after 2 hours.
Embodiment 2
100g deionized water, 4g alkylphenol polyoxyethylene, 4g sodium lauryl sulphate, 2g n-Octanol, 0.06g hydroxylated cellulose, 5g ammonium persulphate and 100g liquid Semen Maydis oil is added successively in the four-hole boiling flask carrying heating and whipping appts.High-speed stirring 10 minutes under normal temperature, obtains Semen Maydis oil emulsion.In above-mentioned Semen Maydis oil emulsion, add 10g diene acrylate under agitation condition, raise temperature of reaction system to 75 DEG C simultaneously, insulation reaction is cooled to normal temperature and namely obtains toughner kernel emulsion based on Semen Maydis oil after 4 hours.
In above-mentioned toughner kernel emulsion, add 10g ammonium persulphate, 20g vinylbenzene and 100g methyl acrylate successively, after high-speed stirring is even, gradually system temperature is increased to 75 DEG C, system temperature was increased to 85 DEG C after 4 hours by insulation reaction further.System is cooled to normal temperature and namely obtains the corn oil base toughner with nucleocapsid structure by continuation insulation reaction after 1 hour.
Embodiment 3
500g deionized water, 15g alkyl, polyether, 10g alkylphenol polyoxyethylene, 10g sodium lauryl sulphate, 10g propyl carbinol, 0.3g sodium alginate, 25g ammonium persulphate and 500g liquid peanut oil is added successively in the stainless steel pressure reactor of jacketed and whipping appts.High-speed stirring 10 minutes under normal temperature, obtains peanut oil emulsion.In above-mentioned peanut oil emulsion, add 50g Vinylstyrene under agitation condition, raise temperature of reaction system to 75 DEG C simultaneously, insulation reaction is cooled to normal temperature and namely obtains toughner kernel emulsion based on peanut oil after 4 hours.
50g peroxy dicarbonate, 100g vinyl cyanide, 400g vinylchlorid and 100g vinylidene chloride is added successively in above-mentioned toughner kernel emulsion, after high-speed stirring is even, gradually system temperature is increased to 50 DEG C, after heat-insulation pressure keeping reaction to system obviously occurs that pressure reduces, continue insulation reaction 1 hour, system is cooled to normal temperature and namely obtains the peanut oil base toughner with nucleocapsid structure.
Embodiment 4
The mixing solutions of 1000g deionized water, 40g alkyl, polyether, 25g tween, 20g sodium laurylsulfonate, 20g lauryl alcohol alcohol, 0.6g carboxy cellulose and 1000g liquid sweet oil and 50g Diisopropyl azodicarboxylate is added successively in the stainless steel pressure reactor of jacketed and whipping appts.High-speed stirring 10 minutes under normal temperature, obtains sweet oil emulsion.In above-mentioned sweet oil emulsion, add 120g diene acrylate under agitation condition, raise temperature of reaction system to 70 DEG C, insulation reaction is cooled to normal temperature and namely obtains olive oil-based toughner kernel emulsion after 4 hours simultaneously.
In above-mentioned toughner kernel emulsion, add 8g peroxy dicarbonate, 15g vinylbenzene, 50g vinylchlorid successively, after high-speed stirring is even, gradually system temperature is increased to 50 DEG C, heat-insulation pressure keeping reacts 30 points.After obviously occurring that pressure reduces to system, continue insulation reaction 1 hour, system is cooled to normal temperature and namely obtains the peanut oil base toughner with nucleocapsid structure.70g peroxy dicarbonate, 130g vinylbenzene and 450g vinylchlorid is added successively in stainless steel pressure holding bottle, mix rear peristaltic meatering pump and the mixed solution in holding bottle is evenly pumped into reactor, be controlled in 1 hour and mixed solution is all pumped into reactor.After heat-insulation pressure keeping reaction obviously occurs Pressure Drop to system, continue reaction 30 minutes.System temperature is cooled to normal temperature, the olive oil base toughner of nucleocapsid structure must be had.
Claims (6)
1. there is a preparation method for the plant oil based toughner of nucleocapsid structure, it is characterized in that the method comprises the following steps:
(1) initiator A consumption be 0 ~ 5% quality than under condition, with emulsifying agent, assistant for emulsifying agent and dispersion agent, liquid vegetable oil is carried out emulsification, obtains the liquid plant fat liquor of particle size range at 10 ~ 400nm;
(2) linking agent is adopted to carry out appropriately crosslinked to emulsified vegetable oil, dosage of crosslinking agent 0 ~ 5% mass ratio;
(3) liquid vegetable oil, high workability monomer and monomer in mass ratio 5 ~ 100:5 ~ 25:5 ~ 100 close with polyvinyl chloride solubility parameter are mixed, and in temperature 0 ~ 90 DEG C and initiator B consumption be 0 ~ 15% quality than condition under polymerization 1 ~ 8 hour, the plant oil based toughner of nucleocapsid structure must be had; Described liquid vegetable oil is at least one in soybean oil, rapeseed oil, Semen Maydis oil, peanut oil, sesame oil, sunflower seed oil, Oleum Gossypii semen, sweet oil, plam oil, Viscotrol C; Described high workability monomer is at least one in vinylbenzene, Vinylstyrene, methyl methacrylate, vinyl cyanide; The described monomer close with polyvinyl chloride solubility parameter is at least one in methyl acrylate, ethyl propenoate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, vinylchlorid, Ethylene Dichloride, vinylidene chloride, vinyl acetate.
2., according to the preparation method described in claim 1 with the plant oil based toughner of nucleocapsid structure, it is characterized in that initiator A is at least one in peroxy dicarbonate, hydrogen peroxide, Potassium Persulphate, ammonium persulphate; Initiator B is at least one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dicumyl peroxide, peroxy dicarbonate, hydrogen peroxide, Potassium Persulphate, ammonium persulphate.
3., according to the preparation method described in claim 1 with the plant oil based toughner of nucleocapsid structure, it is characterized in that emulsifying agent is at least one in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, alkylphenol polyoxyethylene, tween, class of department, alkyl, polyether, sorbeth; Assistant for emulsifying agent is at least one in Virahol, propyl carbinol, the trimethyl carbinol, octanol, enanthol, lauryl alcohol.
4., according to the preparation method described in claim 1 with the plant oil based toughner of nucleocapsid structure, it is characterized in that dispersion agent is at least one in polyvinyl alcohol, methylcellulose gum, hydroxypropylcellulose, HPMC, carboxy cellulose, carboxy cellulose sodium, sodium alginate, gelatin, calcium carbonate, magnesiumcarbonate, talcum powder.
5., according to the preparation method described in claim 1 with the plant oil based toughner of nucleocapsid structure, it is characterized in that linking agent is at least one of Vinylstyrene, diene acrylate, maleic anhydride.
6. according to the plant oil based toughner with nucleocapsid structure that method described in claim 1 obtains.
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| CN108517138A (en) * | 2018-03-30 | 2018-09-11 | 天长市巨龙车船涂料有限公司 | A kind of fire resistant water-based coating |
| CN108641568A (en) * | 2018-03-30 | 2018-10-12 | 天长市巨龙车船涂料有限公司 | A kind of high temperature resistant environment-protective preparation method for coating |
| CN108641569A (en) * | 2018-03-30 | 2018-10-12 | 天长市巨龙车船涂料有限公司 | A kind of environment protecting water-based paint |
| CN108727760A (en) * | 2018-05-10 | 2018-11-02 | 苏州双象光学材料有限公司 | A kind of preparation method of macromolecular PMMA type toughener |
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| CN102295718A (en) * | 2011-05-26 | 2011-12-28 | 北京化工大学 | Bio-based high-branched polyester and preparation method thereof |
| CN102863581A (en) * | 2012-10-19 | 2013-01-09 | 云南大学 | Reactive toughening agent with core-shell structure and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1916046A (en) * | 2005-09-29 | 2007-02-21 | 河北工业大学 | Method for preparing impact modifier of polyvinyl chloride in new type structure of hud |
| CN101338041A (en) * | 2008-04-29 | 2009-01-07 | 夏森林 | PVC environment-protecting asepsis toughening agent |
| CN102234371A (en) * | 2010-04-26 | 2011-11-09 | 深圳市海川实业股份有限公司 | Polymer system based on natural vegetable oil, emulsion, synthesis and application thereof |
| CN102295718A (en) * | 2011-05-26 | 2011-12-28 | 北京化工大学 | Bio-based high-branched polyester and preparation method thereof |
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