CN1618866A - Preparation method of polyvinyl chloride/inorganic rigid particle composite resin - Google Patents
Preparation method of polyvinyl chloride/inorganic rigid particle composite resin Download PDFInfo
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Abstract
A composite resin with high rigidity and impact resistance is prepared from vinyl chloride resin and the high-rigidity inorganic particles with soft polymer layer on their surfaces through suspension polymerizing to otain the composite polyvinyl chloride/rigid inorganic particle resin.
Description
Technical field
The present invention relates to a kind of preparation method of polyvinyl chloride (PVC) RESINS, particularly the preparation method of the polyvinyl chloride (PVC) RESINS of inorganic rigid particle modification.
Background technology
Polyvinyl chloride (PVC) is one of five big general-purpose plastics.After industrialization in 1936, PVC is because good mechanical properties, and production cost is low, and Application Areas is wide and obtain fast development.PVC throughput reaches 2,450 ten thousand tons/year in the world at present.
Owing in the PVC molecular chain a large amount of polarity C-Cl keys is arranged, exist big reactive force between the molecule, so polyvinyl chloride resin is harder, very easily embrittlement under external force.Pure PVC simply supported beam notched Izod impact strength is 2～3kJ/m only
2, can not do structured material and use.In addition, the melt temperature of PVC is 210 ℃, but the C-Cl key in the PVC molecular chain just begins to decompose to deviate from the HCl molecule at 100 ℃, decomposes when temperature is higher than 150 ℃ and quickens.And HCl plays self-catalysis to the degraded of PVC again, and degradation speed is obviously accelerated, and is chain reaction.So the thermostability extreme difference of PVC during forming process, is easily introduced unsaturated link(age) in macromolecular chain, produce crosslinkedly then, worsen the performance of PVC goods.Therefore people have dropped into a large amount of energy and have made improvements, to improve toughness and the thermostability of PVC.
PVC is divided into hard and soft two big classes.Because China's rapid economy development, building and various tubing increase very fast with hard PVC in recent years.Pvc pipe road, door and window and wooden partition will progressively replace traditional metal and timber because of having suitable cost performance.When using PVC as boardy product, the problem that runs into of standing in the breach is a poor toughness.The method of tradition toughening PVC is divided into the toughness reinforcing and physics toughness reinforcing two big classes of chemistry.
The PVC chemistry is toughness reinforcing to be the molecular structure that changes PVC by methods such as grafting, copolymerization, introduces soft segment in the PVC molecular chain.Method commonly used has: (1) vinyl monomer and chloroethylene copolymer, as the copolymerization of vinylchlorid and Octyl acrylate; (2) graft copolymerization of elastomerics and vinylchlorid, as the graft copolymerization of ethylene-propylene rubber(EPR) and vinylchlorid, the graft copolymerization of ethylene-vinyl acetate copolymer (EVA) and vinylchlorid.The advantage of chemical modification is that the toughening modifying effect is remarkable, but has reduced the rigidity of PVC.
Physics is toughness reinforcing to be present the most frequently used method of modifying, and this method is that the compound as toughner is mixed with PVC, and toughner is well dispersed among the PVC, plays toughening effect.The plasticized modifier of hard PVC is a lot, can be divided into elastic body toughening properties-correcting agent and inelastic body plasticized modifier substantially.
The elasticity plasticized modifier mainly contains chlorinatedpolyethylene (CPE), methyl methacrylate-butadiene-styrene ternary graft copolymer (MBS), polyacrylate polymers (ACR), acrylonitrile-butadiene-styrene copolymer (ABS) and ethylene-vinyl acetate copolymer (EVA) etc.
Wherein CPE, MBS and ACR use the most extensively.
The CPE price is lower, and toughening effect is obvious, therefore is widely used.But CPE is made by the high density polyethylene(HDPE) chlorination, not only can cause environmental pollution in the production process, and also can be enclosed with reaction product HCl in the product, quickens PVC goods aging yellowing.Main defective is to be unable to undergo physically aged, and the product innovation performance is fine, but behind the 1-2, shock resistance can drop to original half.
MBS is an impact modifier used when producing the transparent PVC goods, as PVC clear vial, clear sheet, flexible transparent film etc.ACR grafts on the alkyl acrylic ester elastomer with methacrylic acid and the superpolymer that obtains.It and PVC can form power supply, electrophilic is right, thereby compatibility is good, and have superior weathering resistance.When not requiring goods transparent, it is best PVC impact modifier, so be used widely.
MBS and ACR are emulsion copolymers, be " soft nuclear duricrust " type " nuclear-shell " structure on the microtexture, " nuclear " is rubber polymer, and " shell " is methyl methacrylate and styrene polymer, and this " nuclear-shell " structure is often undertaken crosslinked by adding typical cross-linking monomer.What wherein really play impact-resistant modified effect is elastomeric " nuclear ".The purpose that coats " duricrust " on " soft nuclear " surface is to use " duricrust " protection " soft nuclear " of higher glass transition temperature (Tg), prevents " soft nuclear " sticking mutually connection of low Tg.The producer that produces ACR and MBS properties-correcting agent in the world is a lot, mainly contains U.S. Rohmand Hass company, U.S. ATOCHEM company, Britain ICI company, German BASF AG and Japanese clock deep pool chemical company etc.The technology that each company produces MBS and ACR is not quite similar, but roughly comprises following a few step: (1) letex polymerization system styrene-butadiene latex, butadiene latex or butyl acrylate) latex; (2) regulate the latex granularity; (3) with methyl methacrylate, styrene-grafted to latex; (4) aftertreatment.Postprocessing working procedures is more, generally with emulsion flocculation, cooling, centrifugation, washing, filtration, the dry finished product that gets.Perhaps adopt spraying drying to make even-grained particle.
Elastomerics has damaged the intensity and the rigidity of material in toughening modifying, reduced heat-drawn wire.In order to guarantee not reduce its tensile strength and rigidity when improving the PVC impact property, people study and use the inelastic body plasticized modifier.Toughening PVC comprises organic rigid-particle and inorganic rigid particle with non-elastomeric material.
Organic rigid-particle PVC toughner mainly contains acrylonitritrile-styrene resin (AS), polystyrene (PS), methyl methacrylate (PMMA), copolymer of methyl methacrylatestyrene (MMAS), toxilic acid grafted polyethylene (FPE) etc.The inorganic rigid particle toughening PVC mainly uses lime carbonate (CaCO
3), aluminium hydroxide (Al (OH)
3), silicon-dioxide (SiO
2) etc.To discovering of rigid material toughening PVC, though they can play enhancement in toughness reinforcing, toughness reinforcing amplitude is not as elastomerics.
Though PVC has the method for multiple toughening modifying, and the properties-correcting agent kind is numerous, and they or complex process cost an arm and a leg; Performance is not ideal enough.For example the chemical process modification can obtain reasonable toughness-increasing modified material, but the introducing of soft segment has reduced the tensile property of PVC.Though ACR and MBS also have good toughening effect, but the rigidity of PVC can be reduced equally significantly, and also aftertreatments such as complicated involucrum technology, loaded down with trivial details washing, drying, increased the consumption of starting material and energy greatly, cause costing an arm and a leg.By contrast, the low price of CPE also can play toughening effect preferably, and regrettably there are above-mentioned numerous defectives in the toughness reinforcing PVC goods of CPE.CaCO
3Though cheap Deng the inorganic rigid particle toughening PVC, effect is undesirable.In association area, report that both at home and abroad maximum PVC study on the modification is a blending and modifying, reported CaCO as appointing people such as outstanding person, Wu Wei, Yan Shifeng, Hu Shengfei
3Toughening effect to PVC, PVC/CPE, PVC/ACR system.YamachiKazuo etc. add in polymerization, preparation thermostability polyvinyl chloride resin.Patent puts down 6228209, has reported among JapanKokai 72116161, the WO9313145 to add hydrotalcite emulsion, CaCO in suspension polymerization of VC
3Obtain finely dispersed PVC/ hydrotalcite, PVC/CaCO in polyvinyl chloride resin with calcium stearate
3, the compound material of PVC/ calcium stearate.Also there is bibliographical information to adopt the method for in-situ polymerization to prepare PVC/ nanometer CaCO
3Composite building material is resin dedicated.All the inorganic rigid particle surface is modified in the above-mentioned document, but its main purpose is the consistency that increases inorganic rigid particle and PVC, can not improves the shock resistance of PVC well.
Summary of the invention
One of technical issues that need to address of the present invention are to disclose a kind of surface to have organized inorganic rigid particles with the flexible polymer layer of chemical bond form bonding;
Two of the technical issues that need to address of the present invention are the preparation methods that disclose the high inflexible polyvinyl chloride/inorganic rigid particle composite resin of a kind of high-impact, to overcome the above-mentioned defective that prior art exists.
Technical conceive of the present invention is such:
The present invention adopts in-situ polymerization to prepare the inorganic rigid particle modified PVC of bonding compliant interface layer to obtain high tenacity, high-intensity polyvinyl chloride resin based on the toughness reinforcing enhancing polymkeric substance of inorganic rigid particle theory.Promptly unify layer flexible polymer layer, " nuclear-shell " structure organized inorganic rigid particles of preparation " stone soft shell " with the chemical bond formal bond on the inorganic rigid particle surface.Again this particle is joined in-situ polymerization in the PVC suspension polymerization still with vinyl chloride monomer, deionized water, initiator, dispersion agent and other auxiliary agents.Utilize the affinity interaction of vinylchlorid molecule and organized inorganic rigid particles surface molecular, the interface bond strength of Reinforced PVC resin and compliant interface interlayer, and inorganic rigid particle is reached goodly in the polymerization process in position disperse.Compliant interface layer in the compound system can cause crazing when PVC experiences a shock, stop fissured expansion, also can cause the matrix shear yielding under certain morphological structure, thereby consume a large amount of striking energys; Can transmit the external stress of being born preferably again.Reach the purpose of the toughness reinforcing Reinforced PVC of inorganic rigid particle, in the shock resistance that improves PVC, do not reduce the rigidity of PVC.
The organized inorganic rigid particles that said surface has with the flexible polymer layer of chemical bond form bonding is made of the inorganic rigid particle of inside and the flexible polymer layer that is wrapped in outside it, be the organized inorganic rigid particles of " nuclear-shell " structure of a kind of " stone soft shell ", wherein: the thickness of flexible polymer layer is 30nm～100nm;
Said inorganic rigid particle is selected from one or more in lime carbonate, magnesiumcarbonate, silicon-dioxide, titanium dioxide, zinc oxide, Manganse Dioxide, aluminium sesquioxide, Z 250, barium sulfate, calcium sulfate, silicon carbide, silicon nitride, kaolin or the talcum powder;
Said flexible polymer is selected from homopolymer or multipolymer, polyethers or the urethane etc. that contain double bond monomer, preferably at least a polymkeric substance in butyl acrylate, butyl methacrylate, methyl acrylate, methyl methacrylate, glycidyl methacrylate, divinyl, isoprene, vinylbenzene or undecylenic acid or the maleic anhydride, or polyethers, urethane.
The present invention prepares the method for the high inflexible polyvinyl chloride/inorganic rigid particle composite resin of high-impact, comprises the steps:
Organized inorganic rigid particles and vinylchlorid that said surface is had with the flexible polymer layer of chemical bond form bonding adopt suspension polymerization to carry out polymerization, and the weight percent of the various raw materials that adopted is:
Organized inorganic rigid particles 1～30wt%
Vinylchlorid 10～60wt%
Deionized water 30～80wt%
Dispersion agent 0.01～5wt%
Initiator 0.05～5wt%
Buffer reagent 0.05～5wt%
Complexing agent 0.01～5wt%
Chain-transfer agent 0.01～5wt%
Terminator 0.01～5wt%
Preferably include following steps:
Stirred 0.1～2 hour said organized inorganic rigid particles, vinylchlorid, deionized water, dispersion agent, initiator, buffer reagent, complexing agent and chain-transfer agent are cold, being warmed up to 40～80 ℃ is polymerized to pressure and drops to 0.2～1.0MPa, add terminator, adopt conventional method from reaction product, to collect high tenacity, high rush-resistant polyvinyl chloride/inorganic rigid particle composite resin then;
Said dispersion agent is selected from least a in methylhydroxypropylcellulose, hydroxypropylcellulose, polyvinyl alcohol, Polyvinylpyrolidone (PVP), polyethylene oxide fatty acid ester, the ethoxylation polyoxypropylene;
Said initiator is selected from 2, the 2-Diisopropyl azodicarboxylate, 2, the 2-2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), peroxy dicarbonate two (4-tertiary butyl cyclohexyl), di-cyclohexylperoxy dicarbonate, peroxy dicarbonate two (2-ethylhexyl), the two cardamom esters of peroxy dicarbonate, the peroxy dicarbonate di-n-propyl ester, di-isopropyl peroxydicarbonate, peroxy dicarbonate two-2-ethyl phenoxy, the peroxy dicarbonate diisobutyl ester, the two butyl esters of peroxy dicarbonate, the two cetyl of peroxy dicarbonate, peroxidation two (3,5, the own ester of 5-trimethylammonium), peroxidation PIVALIC ACID CRUDE (25) tert-pentyl ester, the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester, peroxidation neodecanoic acid-2,4,4-trimethylammonium pentyl ester, peroxidation neodecanoic acid isopropyl benzene ester, the special butyl ester of peroxidation neodecanoic acid, new peroxide tert-butyl caprate, peroxidation neodecanoic acid-3-hydroxyl-1,1-dimethyl butyl ester, peroxidation neodecanoic acid-1,1,3,3-tetramethyl-butyl ester, the new enanthic acid of peroxidation-3-hydroxyl-1,1-dimethyl butyl ester, the new enanthic acid tert-pentyl ester of peroxidation, the new enanthic acid tert-butyl ester of peroxidation, the new enanthic acid isopropyl benzene of peroxidation ester, the new enanthic acid tert-pentyl ester of peroxidation, peroxidation trimethylacetic acid isopropyl benzene ester, diisobutyryl peroxide, acetyl peroxide cyclohexyl sulfonic acid, peroxidation two different nonanoyls, dilauroyl peroxide, didecanoyl peroxide, peroxidation-2 ethyl hexanoic acid-3-hydroxyl-1,1-dimethyl butyl ester, 2, two (peroxidation of 2-ethyl hexanoyl)-2 of 5-, the 5-dimethylhexane, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidation-2 ethyl hexanoic acid tert-pentyl ester, tertbutyl peroxide, in the dibenzoyl peroxide one or more;
Said buffer reagent is selected from a kind of in Trisodium Citrate, ammoniacal liquor, Sodium phosphate dibasic, dipotassium hydrogen phosphate, saleratus, sodium bicarbonate or the bicarbonate of ammonia;
Said complexing agent is selected from EDTA disodium salt, EDTA sodium calcium salt, Sodium Nitrite or trisodium citrate;
Said chain-transfer agent is selected from carbon tetrabromide, bromo-trichloromethane, tetracol phenixin, 2 cbloropropane isopropyl chloride, chloroform, ethylene dichloride, methylene dichloride, monochloroethane, 1,1,2,2-tetrachloroethane, 2,4-dichloropentane, trieline, 2,4, a kind of in 6-three chloroheptanes;
Said terminator is selected from tetrachlorobenzoquinone, para benzoquinone, anthraquinone, p-ten.-butylcatechol, 2,5-two tert-pentyl Resorcinol, biphenyl is to amine, Resorcinol, dihydroxyphenyl propane, Meta-dinitrobenzene, 2, the 4-dinitrobenzene, 1,3, the 5-trinitrobenzene, the N nitrosodiphenylamine, nitrosobenzene, nitroso-, monomethylaniline, sulphur fork pentanoic, dithio dibenzoyl disulfide thing, the acetone semicarbazone thiocarbamide, 1,1-phenylbenzene-2-cumyl hydrazine, 2,2,6,6-tetramethyl--4-hydroxy piperidine nitroxyl free radical, iron trichloride, titanous chloride, a kind of in cupric chloride or the sulphur;
Said surface has with one of preparation method of the organized inorganic rigid particles of the flexible polymer layer of chemical bond form bonding and comprises the steps:
Inorganic rigid particle is dispersed in the deionized water, dropping is with 5～25wt% coupling agent, fully reaction is 0.1～5 hour, be warmed up to 60～90 ℃, drip 1～15wt% emulsifier aqueous solution, continue to stir 0.1～3 hour, divide two-way to drip the aqueous solution that 30～200wt% contains double bond monomer and 0.05～3wt% letex polymerization initiator and 1～15wt% emulsifier mixture then, drip off in 1～2 hour, 60～90 ℃ were reacted 0.5～5 hour, divide two-way to drip the aqueous solution that 30～200wt% contains double bond monomer and 0.05～3wt% initiator and 1～15wt% emulsifier mixture again, drip off in 1～2 hour, 60～90 ℃ were reacted 1～5 hour.Add 0.05～1wt% letex polymerization initiator solution, continue " nuclear-shell " structure organized inorganic rigid particles emulsion that reaction obtained " stone soft shell " in 0.5～2 hour;
The raw material that adds in the reaction process is a benchmark with the weight of inorganic rigid particle all;
Said surface has with the preparation method's of the organized inorganic rigid particles of the flexible polymer layer of chemical bond form bonding two and comprises the steps:
0.1～5wt% coupling agent and inorganic rigid particle were disperseed in high-speed mixer 0.1～1 hour, add solvent then, stirred 0.1～1 hour, be warmed up to 60～90 ℃, drip 30～200wt% and contain double bond monomer and 0.05～3wt% polymerization starter, dripped off in 1～2 hour, and continued reaction 1～6 hour, from reaction product, collect " nuclear-shell " structure organized inorganic rigid particles of " stone soft shell " then;
The solvent of being addressed is selected from least a in vinyl acetic monomer, N-BUTYL ACETATE, benzene, toluene or the dimethylbenzene;
The raw material that adds in the reaction process is a benchmark with the weight of inorganic rigid particle all.
In method one and the method two:
The coupling agent of being addressed is selected from organic acid, silane coupling agent, titanate coupling agent, phosphate coupling agent or the aluminate coupling agent that has unsaturated double-bond;
The organic acid that has unsaturated double-bond is selected from vinylformic acid, methacrylic acid or toxilic acid or its homopolymer and multipolymer;
Silane coupling agent is selected from vinyltrimethoxy silane, vinyltriethoxysilane, γ-chloropropyl trichloro-silane, γ-r-chloropropyl trimethoxyl silane, γ-chloropropyl triethoxysilane, γ-methacryloxypropyl trimethoxy silane, Alpha-Methyl acryloxy Union carbide A-162 or trimethylene isocyanate group Trimethoxy silane, trimethylene isocyanate group triethoxyl silane.
Titanate coupling agent is selected from sec.-propyl three oleoyl titanic acid ester; sec.-propyl triacryl titanic acid ester; sec.-propyl two (dodecyl tetradecyl) methacryloyl titanic acid ester; sec.-propyl dodecyl tetradecyl methacryloyl titanic acid ester; sec.-propyl distearyl ylmethyl acryl ester titanic acid ester; sec.-propyl dimethyl allene acidic group isostearoyl base titanic acid ester; sec.-propyl trimethylammonium acryl titanic acid ester; sec.-propyl two isostearoyl base acryl titanic acid ester; isopropyl stearyl-two acryl titanic acid ester; sec.-propyl triacryl titanic acid ester; isostearoyl ylmethyl acryl oxo ethanoyl titanic acid ester; two (methacryloyl) methyl oxyacetate titanate coupling agent; dimethyl propylene enoyl-oxo ethanoyl titanic acid ester; two acryl oxo ethanoyl titanic acid ester; methacryloyl isostearoyl base ethylene two oxy titanic acid ester; dimethyl propylene enoyl-ethylene two oxy titanic acid ester or two acryl ethylene oxide,1,2-epoxyethane base titanic acid ester.
Phosphate coupling agent is selected from four (2,2 two allyl oxygen methyl isophthalic acid-butenyls) two (2-three decyl phosphorous acid ester groups) titanic acid ester, methacrylic acid diethoxy phosphate coupling agent.
Aluminate coupling agent is selected from two (oleic acid Diethylene Glycol ester group) aluminic acid isopropyl ester, two allyl oxygen methyl phosphorodithioates close aluminium.
The emulsifying agent of addressing is selected from sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, alkyl oxy DAADBSA disodium, dodecyl alcohol sodium sulfate, sodium lauryl sulphate, ammonium lauryl sulfate, 2-second sodium hexy1 sulfate, tridecyl sodium sulfate, ethoxylated alkyl ether ammonium sulfate, straight chain ethoxylated alkyl ether ammonium sulfate, the alkyl oxide sodium sulfosuccinate, phenolic group ether sulfosuccinic acid in ninth of the ten Heavenly Stems sodium, ethoxylated alkylphenol ammonium sulfate, at least a in the cetyl trimethylammonium bromide;
The letex polymerization initiator of being addressed is selected from ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide, tertbutyl peroxide, isopropyl phenyl hydrogen peroxide, cumyl hydroperoxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, 4, a kind of in 4 '-azo two-(the 4-cyanopentanoic acid).
The weight concentration of emulsifier aqueous solution is 10～80%;
The weight concentration of letex polymerization initiator solution is 10～80%;
Said surface has with the preparation method's of the organized inorganic rigid particles of the flexible polymer layer of chemical bond form bonding three and comprises the steps:
The coupling agent that 5～100wt% is contained long flexible chain adds inorganic rigid particle, disperses in high-speed mixer 0.1～1 hour, obtains " nuclear-shell " structure organized inorganic particle of " stone soft shell ";
The raw material that adds in the reaction process is a benchmark with the weight of inorganic rigid particle all.
The coupling agent of being addressed that contains long flexible chain is selected from butyl polyacrylate base Trimethoxy silane; the polyethylene oxide base; poly(propylene oxide) base Trimethoxy silane; ethylene oxide type polyurethane-base Trimethoxy silane; propylene oxide type polyurethane base Trimethoxy silane; butyl polyacrylate ethyl triethoxy silicane alkane; polyethylene oxide ethyl triethoxy silicane alkane; poly(propylene oxide) ethyl triethoxy silicane alkane; ethylene oxide type polyurethane-base triethoxyl silane; propylene oxide type polyurethane ethyl triethoxy silicane alkane; butyl polyacrylate base dipyrophosphoric acid ester acyl group oxyacetate titanate; polyethylene oxide base dipyrophosphoric acid ester acyl group oxyacetate titanate; poly(propylene oxide) base dipyrophosphoric acid ester acyl group oxyacetate titanate; ethylene oxide type polyurethane-base dipyrophosphoric acid ester acyl group oxyacetate titanate; propylene oxide type polyurethane base dipyrophosphoric acid ester acyl group oxyacetate titanate; butyl polyacrylate base pyrophosphate acyl group oxo ethanoyl titanic acid ester; polyethylene oxide base pyrophosphate acyl group oxo ethanoyl titanic acid ester; poly(propylene oxide) base pyrophosphate acyl group oxo ethanoyl titanic acid ester; butyl polyacrylate base pyrophosphate acyl group oxo ethanoyl titanic acid ester; polyethylene oxide base pyrophosphate acyl group oxo ethanoyl titanic acid ester; poly(propylene oxide) base pyrophosphate acyl group oxo ethanoyl titanic acid ester; ethylene oxide type polyurethane-base pyrophosphate acyl group oxo ethanoyl titanic acid ester; propylene oxide type polyurethane base pyrophosphate acyl group oxo ethanoyl titanic acid ester; butyl polyacrylate two (2-three decyl phosphorous acid ester groups) titanic acid ester; polyethylene oxide two (2-three decyl phosphorous acid ester groups) titanic acid ester; poly(propylene oxide) two (2-three decyl phosphorous acid ester groups) titanic acid ester; ethylene oxide type polyurethane-base two (2-three decyl phosphorous acid ester groups) titanic acid ester; propylene oxide type polyurethane base two (2-three decyl phosphorous acid ester groups) titanic acid ester; propylene dimer acid butyl ester base pyrophosphate acyl group oxo ethanoyl titanic acid ester; dimerization Oxyranyle pyrophosphate acyl group oxo ethanoyl titanic acid ester; two poly(propylene oxide) base pyrophosphate acyl group oxo ethanoyl titanic acid ester; diepoxide for example type polyurethane base pyrophosphate acyl group oxo ethanoyl titanic acid ester; diepoxy propane type polyurethane base pyrophosphate acyl group oxo ethanoyl titanic acid ester; propylene dimer acid butyl ester phosphoric acid ester is closed aluminium; two polyethylene oxide phosphoric acid ester are closed aluminium; two poly(propylene oxide) phosphoric acid ester are closed aluminium; diepoxide for example type polyurethane phosphoric acid ester is closed aluminium; diepoxy propane type polyurethane phosphoric acid ester is closed aluminium; propylene dimer acid butyl ester base aluminic acid isopropyl ester; dimerization Oxyranyle aluminic acid isopropyl ester; two poly(propylene oxide) base aluminic acid isopropyl esters; diepoxide for example type polyurethane base aluminic acid isopropyl ester; a kind of in the diepoxy propane type polyurethane base aluminic acid isopropyl ester.
The high inflexible PVC/ of the high-impact inorganic rigid particle composite resin that adopts method of the present invention to obtain, compliant interface layer in the compound system can cause crazing when PVC experiences a shock, stop fissured expansion, under certain morphological structure, also can cause the matrix shear yielding, thereby consume a large amount of striking energys; Can transmit the external stress of being born preferably again.Reach the purpose of the toughness reinforcing Reinforced PVC of inorganic rigid particle, in the shock resistance that improves PVC, do not reduce the rigidity of PVC.Make synthetic polyvinyl chloride resin need not to add toughner such as ACR, can be directly used in the manufacturing of plastic door-window etc.
Embodiment
The present invention will be specifically described by embodiment hereinafter, adopt following testing method in an embodiment:
The mensuration of inorganic rigid particle surface bond rate: with solvent extraction 24 hours, remove the polymkeric substance on the bonding not, go up the bonding rate of surveying at thermogravimetric analyzer (TG) after the vacuum-drying.Calculation formula is:
Wherein, W
1Be the quality of sample before weightless, W
2Quality for inorganic rigid particle residual after the polymer unwinds.
Inorganic rigid particle surface covered effect is observed: it is 1% deionized water or solvent suspension liquid that the inorganic rigid particle after the extracting is made into concentration, drip suspension liquid on the copper mesh of band supporting film, drying is placed on whether observation inorganic rigid particle surface is coated with polymkeric substance under the transmission electron microscope (TEM).
The Mechanics Performance Testing of PVC/ inorganic rigid particle composite resin:
The PVC/ inorganic rigid particle composite resin is prepared burden according to table 1.Thiol organotin stablizer Mark7216GV; Processing aid B863, its chemical name are styrene-acrylonitrile copolymer; Internal lubricant EBS, its chemical name are N, N '-ethylene two (12-hydroxyl stearylamide), and oxidation inhibitor U641, its chemical name are 2,4,6-three tert-butylbenzenes, the 2-butyl, the 2-ethyl, 1, ammediol phosphoric acid salt is U.S. GE company product.The compound for preparing is poured into and is mixed 10min in the high-speed mixer, then in two roller mills 170 ℃ open refining 10min, last on platen-press 180 ℃ be pressed into the thick sheet material of 4mm.
Table 1.PVC processing formula (part)
PVC or
Organotin stabilizer B863 EBS U641 polyethylene wax
The PVC compound resin
100 3 1 0.6 0.1 0.6
With the sheet material made tensile strength and notched Izod impact strength according to GB GB/T1040-92, GB/T1043-93 test material.
Embodiment 1
Get 10%CaCO
3Aqueous suspension 1200g, CaCO
3Particle diameter is 30～40nm, ultra-sonic dispersion 15 minutes.Drip 6g vinylformic acid (AA), stirred 30 minutes.Be warmed up to 85 ℃ and drip 4.6g ethoxylated alkylphenol ammonium sulfate (CO436) (admittedly containing 58%), continue to stir 30 minutes.Divide two-way to drip 60g butyl acrylate (BA) and (0.3g ammonium persulphate (APS)+2.3gCO436+15g deionized water) then, drip off in 1 hour, 85 ℃ are incubated 0.5 hour.Divide two-way to drip 60gBA and (0.3gAPS+2.3gCO436+15g deionized water) again, continue reaction and obtained CaCO in 1 hour
3/ PBA organized inorganic rigid particles emulsion.
Get the above-mentioned CaCO of 200g
3The oven dry of/PBA organized inorganic rigid particles emulsion, recording the bonding rate after 24 hours with the vinyl acetic monomer extracting on thermogravimetric analyzer is 80%, observes CaCO under the transmission electron microscope
3Particle surface is enclosed with the thick polymkeric substance of the about 30nm of one deck.
At above-mentioned CaCO
3Add 1600g vinylchlorid (VC), 2900g deionized water, 1.61g Vltra tears in the/PBA organized inorganic rigid particles emulsion, 1.92g polyvinyl alcohol, 2.5g peroxy dicarbonate two (2-ethylhexyl), 5g 2,2'-Azobis(2,4-dimethylvaleronitrile), 0.3g (NH
4) HCO
3, 0.3gEDTA disodium salt, 0.5g carbon tetrabromide, cold stirring 30 minutes is warmed up to 57.5 ℃ and is polymerized to pressure and drops to 0.4MPa, adds the 0.83g tetrachlorobenzoquinone, reclaims unreacted VC.Discharging, washing, centrifuge dehydration, 60 ℃ of oven dry obtain high tenacity, high-impact PVC/CaCO
3Compound resin, wherein CaCO
3Content is about 8%.
This PVC compound resin is opened refining 10 minutes according to 170 ℃ of the prescriptions of table 1, then on platen-press 180 ℃ be pressed into the thick sheet material of 4mm, the notched Izod impact strength of test material is 25.0kJ/m
2, be 7.1 times of pure polyvinyl chloride resin; The tensile strength of material is 61.2MPa, and is suitable with the 59.8MPa of pure polyvinyl chloride resin.Data show that the method that adopts the inorganic rigid particle modification can prepare the polyvinyl chloride resin of high tenacity, high rigidity.
Embodiment 2
Get 120gSiO
2High speed dispersion in the 1180g deionized water, SiO
2Particle diameter is 10～20nm, and ultra-sonic dispersion is 15 minutes again.Drip 3g vinyltrimethoxy silane coupling agent, stirred 40 minutes.Be warmed up to 80 ℃ and drip the 7.0g Sodium dodecylbenzene sulfonate, continue to stir 40 minutes.Divide two-way to drip (40g isoprene (IP)+20g butyl acrylate (BA)) and (0.3g Potassium Persulphate (KPS)+3.5g Sodium dodecylbenzene sulfonate+15g deionized water) then, drip off in 1 hour, 80 ℃ are incubated 0.5 hour.Divide two-way to drip (10g isoprene (IP)+50g butyl acrylate (BA)) and (0.3gKPS+3.5g sodium laurylsulfonate+15g deionized water) again, continue reaction and obtained SiO in 1 hour
2/ PIP/PBA organized inorganic rigid particles emulsion.
Get the above-mentioned SiO of 200g
2The oven dry of/PIP/PBA organized inorganic rigid particles emulsion, recording the bonding rate after 24 hours with the N-BUTYL ACETATE extracting on thermogravimetric analyzer is 80%, observes SiO under the transmission electron microscope
2Particle surface is enclosed with the thick polymkeric substance of the about 50nm of one deck.
At above-mentioned SiO
2Add 1600g vinylchlorid (VC), 2900g deionized water, 1.8g hydroxypropylcellulose, 1.92g Polyvinylpyrolidone (PVP), 4.0g peroxy dicarbonate two (4-tertiary butyl cyclohexyl), 2.0g 2,2'-Azobis(2,4-dimethylvaleronitrile), 0.3gNaHCO in the/PIP/PBA organized inorganic rigid particles emulsion
3, 0.3gEDTA sodium calcium salt, 1.0g chloroform, cold stirring 30 minutes is warmed up to 60 ℃ and is polymerized to pressure and drops to 0.45MPa, adds the 0.83g Resorcinol, reclaims unreacted VC.Discharging, washing, centrifuge dehydration, 50 ℃ of oven dry obtain high tenacity, high-impact PVC/SiO
2Compound resin, wherein SiO
2Content is about 8%.
This PVC compound resin is opened refining 10 minutes according to 170 ℃ of the prescriptions of table 1, then on platen-press 180 ℃ be pressed into the thick sheet material of 4mm, the notched Izod impact strength of test material is 23.4kJ/m
2, be 7.5 times of pure polyvinyl chloride resin; The tensile strength of material is 55.2MPa, and is suitable with the 53.8MPa of pure polyvinyl chloride resin.Data show that the method that adopts the inorganic rigid particle modification can prepare the polyvinyl chloride resin of high tenacity, high rigidity.
Embodiment 3
Get 120gTiO
2Be distributed in the 1180g deionized water TiO
2Particle diameter is 80～100nm.Drip 3.6g two (methacryloyl) methyl oxyacetate titanate coupling agent (KHT-305), stirred 30 minutes.Be warmed up to 75 ℃ of branch two-way and drip (40g undecylenic acid (HA)+20g methyl acrylate (MA)) and (0.3g Sodium Persulfate (NaPS)+8.5g dodecyl alcohol sodium sulfate+15g deionized water), drip off in 1 hour, 85 ℃ are incubated 1 hour.Divide two-way to drip (10gMA+50g butyl acrylate (BA)) and (0.3g hydrogen peroxide+8.5g lauryl mercaptan acid sodium+15g deionized water) again, continue reaction and obtained TiO in 1 hour
2/ PHA/PMA/PBA organized inorganic rigid particles emulsion.
Get the above-mentioned TiO of 200g
2The oven dry of/PHA/PMA/PBA organized inorganic rigid particles emulsion, recording the bonding rate after 24 hours with the acetone extracting on thermogravimetric analyzer is 83.5%, observes TiO under the transmission electron microscope
2Particle surface is enclosed with the thick polymkeric substance of the about 100nm of one deck.
At above-mentioned TiO
2Add 1600g vinylchlorid (VC), 3500g deionized water, 3.4g polyvinyl alcohol in the/PHA/PMA/PBA organized inorganic rigid particles emulsion, 1.2g Polyvinylpyrolidone (PVP), 4.5g peroxidation two (3,5, the own ester of 5-trimethylammonium), 2.5g peroxidation PIVALIC ACID CRUDE (25) tert-pentyl ester, 0.4gNaHCO
3, 0.5g Sodium Nitrite, 1.5g monochloroethane, cold stirring 30 minutes is warmed up to 53 ℃ and is polymerized to pressure and drops to 0.38MPa, adds the 0.75g dihydroxyphenyl propane, reclaims unreacted VC.Discharging, washing, centrifuge dehydration, 60 ℃ of oven dry obtain high tenacity, high-impact PVC/TiO
2Compound resin, wherein TiO
2Content is about 8%.
This PVC compound resin is opened refining 10 minutes according to 170 ℃ of the prescriptions of table 1, then on platen-press 180 ℃ be pressed into the thick sheet material of 4mm, the notched Izod impact strength of test material is 20.3kJ/m
2, be 6 times of pure polyvinyl chloride resin; The tensile strength of material is 58.4MPa, increases than pure polyvinyl chloride resin.Data show that the method that adopts the inorganic rigid particle modification can prepare the polyvinyl chloride resin of high tenacity, high rigidity.
Embodiment 4
Get the MgCO that the 100g particle diameter is 30～60nm
3, high speed dispersion is in the 1000g deionized water, and ultra-sonic dispersion is 15 minutes again.Add the 10g MALEIC ANHYDRIDE, stir on the limit, heats up in the limit, and 60 ℃ are incubated 30 minutes.When continuing to be warmed up to 85 ℃, divide two-way to drip 40g butyl acrylate (BA) and (0.25g isopropyl phenyl hydrogen peroxide+6.7g straight chain ethoxylated alkyl ether ammonium sulfate+15g deionized water), drip off in 1 hour, 85 ℃ are incubated 1 hour.Divide two-way Dropwise 5 0g butyl acrylate (BA) and (0.25g isopropyl phenyl hydrogen peroxide+6.7g straight chain ethoxylated alkyl ether ammonium sulfate+15g deionized water) again, continue reaction and obtained in 1 hour.
Get the above-mentioned MgCO of 200g
3The oven dry of/PBA organized inorganic rigid particles emulsion, recording the bonding rate after 24 hours with the benzene extracting on thermogravimetric analyzer is 78%, observes MgCO under the transmission electron microscope
3Particle surface is enclosed with the thick polymkeric substance of the about 60nm of one deck.
At above-mentioned MgCO
3Add 1600g vinylchlorid (VC), 2900g deionized water, 4.2g polyvinyl alcohol, 0.9g polyethylene oxide fatty acid ester, 6.0g peroxidation neodecanoic acid isopropyl benzene ester, 1.8g peroxidation two different nonanoyls, 0.4gNaHCO in the/PBA organized inorganic rigid particles emulsion
3, 0.5g trisodium citrate, 1.5g trieline, cold stirring 30 minutes is warmed up to 50.5 ℃ and is polymerized to pressure and drops to 0.35MPa, adds the 0.75g Meta-dinitrobenzene, reclaims unreacted VC.Discharging, washing, centrifuge dehydration, 60 ℃ of oven dry obtain high tenacity, high-impact PVC/MgCO
3Compound resin, wherein MgCO
3Content is about 6%.
This PVC compound resin is opened refining 10 minutes according to 170 ℃ of the prescriptions of table 1, then on platen-press 180 ℃ be pressed into the thick sheet material of 4mm, the notched Izod impact strength of test material is 17.6kJ/m
2, be 4.6 times of pure polyvinyl chloride resin; The tensile strength of material is 51.3MPa, increases than pure polyvinyl chloride resin.Data show that the method that adopts the inorganic rigid particle modification can prepare the polyvinyl chloride resin of high tenacity, high rigidity.
Embodiment 5
Get the ZnO that the 100g particle diameter is 60～80nm, add 3g methacrylic acid diethoxy phosphate coupling agent, disperseed 15 minutes oven dry in the high-speed mixer.Join then in the 1000g benzene solvent, stirred 30 minutes, and be warmed up to 75 ℃, drip 60g butyl methacrylate (MBA), 20g vinylbenzene (St), 20g methyl methacrylate (MMA) and 0.84g 2,2'-Azobis(2,4-dimethylvaleronitrile) mixture, dripped off in 2 hours, and continued reaction 3 hours.Water pump is extracted solvent benzol out, pours out when system viscosity is big.Vacuum drying obtains the organized inorganic rigid particles.
Get the above-mentioned ZnO/PMBA/PS/PMMA organized inorganic of 20g rigid particles, adopting thermogravimetry to measure the bonding rate after 24 hours with the benzene extracting is 74%, observes ZnO under the transmission electron microscope (TEM) and is coated with the thick polymkeric substance of the about 50nm of one deck.
With the above-mentioned ZnO/PMBA/PS/PMMA organized inorganic of 140g rigid particles, 1600g vinylchlorid (VC), 4000g deionized water, 1.61g Vltra tears, 1.92g polyvinyl alcohol, the special butyl ester of 3.2g peroxidation neodecanoic acid, 5g2, two (peroxidation of 2-ethyl hexanoyl)-2 of 5-, 5-dimethylhexane, 1.5g1,1,2,2-tetrachloroethane, 0.3g (NH
4) HCO
3, the 0.3gEDTA disodium salt, cold stirring 30 minutes is warmed up to 57.5 ℃ and is polymerized to pressure and drops to 0.4MPa, adds 0.83g aminomethyl phenyl amine, reclaims unreacted VC.Discharging, washing, centrifuge dehydration, 60 ℃ of oven dry obtain high tenacity, high-impact PVC/CaCO
3Compound resin, wherein ZnO content is about 4%.
This PVC compound resin is opened refining 10 minutes according to 170 ℃ of the prescriptions of table 1, then on platen-press 180 ℃ be pressed into the thick sheet material of 4mm, the notched Izod impact strength of test material is 15.7kJ/m
2, be 4.5 times of pure polyvinyl chloride resin; The tensile strength of material is 64.7MPa, and is slightly high with the 59.8MPa of pure polyvinyl chloride resin.Data show that also the method that adopts the inorganic rigid particle modification can prepare the polyvinyl chloride resin of high tenacity, high rigidity.
Embodiment 6
14g γ-glycidyl ether oxygen propyl trimethoxy silicane is sneaked in the 100g water, be added in the talcum powder that the 140g particle diameter is 10 μ m, disperseed 15 minutes in the high-speed mixer, oven dry.Talcum powder after the oven dry joins in the 600g xylene solvent, stirs 30 minutes, is warmed up to 75 ℃.Drip 40g methyl methacrylate (MMA), 80g divinyl (Bd), 20g vinylbenzene (St), 28g glycidyl methacrylate (GMA) and 0.84g 2,2'-Azobis(2,4-dimethylvaleronitrile) mixture, dripped off in 2 hours, continue reaction 3 hours.Water pump is extracted solvent xylene out, pours out when system viscosity is big.Vacuum drying obtains talcum powder/MBS organized inorganic rigid particles.
Get the above-mentioned talcum powder of 20g/MBS organized inorganic rigid particles, adopting the thermogravimetric method to measure the bonding rate after 24 hours with the dimethylbenzene extracting is 79%, observes the talcum powder particle surface under the transmission electron microscope and is enclosed with the thick polymkeric substance of the about 100nm of one deck.
With the above-mentioned talcum powder of 250g/MBS organized inorganic rigid particles, 1600g vinylchlorid (VC), 4000g deionized water, 1.61g Vltra tears, 1.92g polyvinyl alcohol, the two cardamom esters of 2.5g peroxy dicarbonate, 5g tertbutyl peroxide, 2.0g 2,4-dichloropentane, 0.3g (NH
4) HCO
3, the 0.3gEDTA disodium salt, cold stirring 30 minutes is warmed up to 57.5 ℃ and is polymerized to pressure and drops to 0.4MPa, adds the 0.83g Meta-dinitrobenzene, reclaims unreacted VC.Discharging, washing, centrifuge dehydration, 60 ℃ of oven dry obtain high tenacity, high-impact PVC/ talcum powder compound resin, and wherein talcum powder content is about 8%.
This PVC compound resin is opened refining 10 minutes according to 170 ℃ of the prescriptions of table 1, then on platen-press 180 ℃ be pressed into the thick sheet material of 4mm, the notched Izod impact strength of test material is 16.3kJ/m
2, be 4.6 times of pure polyvinyl chloride resin; The tensile strength of material is 66.5MPa, has improved 11.2% with the 59.8MPa of pure polyvinyl chloride resin.Data show that equally the method that adopts the modification of organized inorganic rigid particles can prepare the polyvinyl chloride resin of high tenacity, high rigidity.
Embodiment 7
140g two poly(propylene oxide) base aluminic acid isopropyl ester coupling agents are mixed with 70g alcohol, 70g water, and wherein the molecular weight of poly(propylene oxide) side chain is 1.2 ten thousand.Said mixture is added in the kaolin that the 140g particle diameter is 2 μ m, disperseed 15 minutes in the high-speed mixer, obtain kaolin/poly(propylene oxide) organized inorganic rigid particles.
Get the above-mentioned kaolin of 20g/poly(propylene oxide) organized inorganic rigid particles, adopting the thermogravimetric method to measure the bonding rate after 24 hours with the acetone extracting is 70%, observes the kaolin particle surface under the transmission electron microscope and is enclosed with the thick polymkeric substance of the about 100nm of one deck.
With the above-mentioned kaolin of 240g/polyethers organized inorganic rigid particles, 1600g vinylchlorid (VC), 4000g deionized water, 1.61g Vltra tears, 1.92g polyvinyl alcohol, the new enanthic acid of 2.5g peroxidation-3-hydroxyl-1,1-dimethyl butyl ester, 2.0g dibenzoyl peroxide, 3.0g 2,4,6-three chloroheptanes, 0.3g (NH
4) HCO
3, the 0.3gEDTA sodium calcium salt, cold stirring 30 minutes is warmed up to 57.5 ℃ and is polymerized to pressure and drops to 0.4MPa, adds the 0.83g Resorcinol, reclaims unreacted VC.Discharging, washing, centrifuge dehydration, 58 ℃ of oven dry obtain high tenacity, high-impact PVC/ kaolin compound resin, and wherein kaolin content is about 8%.
This PVC compound resin is opened refining 10 minutes according to 170 ℃ of the prescriptions of table 1, then on platen-press 180 ℃ be pressed into the thick sheet material of 4mm, the notched Izod impact strength of test material is 19.8kJ/m
2, be 5.7 times of pure polyvinyl chloride resin; The tensile strength of material is 63.5MPa, and is suitable with the 59.8MPa of pure polyvinyl chloride resin.Data show that equally the method that adopts the modification of organized inorganic rigid particles can prepare the PV resin of high tenacity, high rigidity.
Embodiment 8
80g ethylene oxide type polyurethane-base pyrophosphate acyl group oxo ethanoyl titanate coupling agent is mixed with 30g alcohol, 30g water, and wherein the molecular weight of polyurethane branch chains is 2.0 ten thousand.Said mixture is added to the Al that the 40g particle diameter is 1 μ m
2O
3With the 40g particle diameter be in the kaolinic mixture of 2 μ m, disperseed in the high-speed mixer 15 minutes, obtain Al
2O
3-kaolin/urethane organized inorganic rigid particles.
Get the above-mentioned Al of 20g
2O
3-kaolin/urethane organized inorganic rigid particles adopts the thermogravimetric method to measure the bonding rate with the acetone extracting and is 73%, observes Al under the transmission electron microscope after 24 hours
2O
3Particle surface is enclosed with the thick polymkeric substance of the about 100nm of one deck.
With the above-mentioned Al of 120g
2O
3-kaolin/urethane organized inorganic rigid particles, 1600g vinylchlorid (VC), 4000g deionized water, 1.61g Vltra tears, 1.92g polyvinyl alcohol, 2.5g peroxy dicarbonate two (2-ethylhexyl), 5g 2,2'-Azobis(2,4-dimethylvaleronitrile), 1.0g bromo-trichloromethane 0.3g, (NH
4) HCO
3, the 0.3gEDTA sodium calcium salt, cold stirring 30 minutes is warmed up to 57.5 ℃ and is polymerized to pressure and drops to 0.3MPa, adds the 0.83g Resorcinol, reclaims unreacted VC.Discharging, washing, centrifuge dehydration, 62 ℃ of oven dry obtain high tenacity, high-impact PVC/Al
2O
3-kaolin compound resin, wherein Al
2O
3-kaolin content is about 4%.
This PVC compound resin is opened refining 10 minutes according to 170 ℃ of the prescriptions of table 1, then on platen-press 180 ℃ be pressed into the thick sheet material of 4mm, the notched Izod impact strength of test material is 14.9kJ/m
2, be 4.3 times of pure polyvinyl chloride resin; The tensile strength of material is 60.5MPa, and is suitable with the 59.8MPa of pure polyvinyl chloride resin.Data show that equally the method that adopts the inorganic rigid particle modification can prepare the polyvinyl chloride resin of high tenacity, high rigidity.
Embodiment 9
140g butyl polyacrylate base Trimethoxy silane coupling agent is mixed with 30g alcohol, 30g water, and wherein the molecular weight of butyl polyacrylate side chain is 0.8 ten thousand.Said mixture is added to the CaSO that the 120g particle diameter is 50～70nm
4In, disperseed 25 minutes in the high-speed mixer, obtain CaSO
4/ butyl polyacrylate organized inorganic rigid particles.
Get the above-mentioned CaSO of 20g
4/ butyl polyacrylate organized inorganic rigid particles adopts the thermogravimetric method to measure the bonding rate with the vinyl acetic monomer extracting and is 87%, observes CaSO under the transmission electron microscope after 24 hours
4Particle surface is enclosed with the thick polymkeric substance of the about 100nm of one deck.
With the above-mentioned CaSO of 240g
4/ butyl polyacrylate organized inorganic rigid particles, 1600g vinylchlorid (VC), 3500g deionized water, 2.10g ethoxylation polyoxypropylene, 1.50g polyvinyl alcohol, 4.0g peroxy dicarbonate two-2-ethyl phenoxy, 2.8g tertbutyl peroxide, 1.2g 2,4,6-three chloroheptanes, 0.5g dipotassium hydrogen phosphate, 0.5g Sodium Nitrite, cold stirring 30 minutes is warmed up to 62 ℃ and is polymerized to pressure and drops to 0.28MPa, add 0.6g N nitrosodiphenylamine, reclaim unreacted VC.Discharging, washing, centrifuge dehydration, 55 ℃ of oven dry obtain high tenacity, high-impact PVC/CaSO
4Compound resin, wherein CaSO
4Content is about 7%.
This PVC compound resin is opened refining 10 minutes according to 170 ℃ of the prescriptions of table 1, then on platen-press 180 ℃ be pressed into the thick sheet material of 4mm, the notched Izod impact strength of test material is 19.4kJ/m
2, be 5.6 times of pure polyvinyl chloride resin; The tensile strength of material is 58.1MPa, and is suitable with the 59.8MPa of pure polyvinyl chloride resin.Data show that equally the method that adopts the modification of organized inorganic rigid particles can prepare the polyvinyl chloride resin of high tenacity, high rigidity.
Claims (10)
1. a surface has the organized inorganic rigid particles with the flexible polymer layer of chemical bond form bonding, it is characterized in that, be made of the inorganic rigid particle of inside and the flexible polymer layer that is wrapped in outside it, the thickness of flexible polymer layer is 30nm～100nm;
Said inorganic rigid particle is selected from one or more in lime carbonate, magnesiumcarbonate, silicon-dioxide, titanium dioxide, zinc oxide, Manganse Dioxide, aluminium sesquioxide, Z 250, barium sulfate, calcium sulfate, silicon carbide, silicon nitride, kaolin or the talcum powder.
Said flexible polymer is selected from homopolymer or multipolymer, polyethers or the urethane that contains double bond monomer.
2. organized inorganic rigid particles according to claim 1, it is characterized in that, said flexible polymer is selected from polymkeric substance at least a in butyl acrylate, butyl methacrylate, methyl acrylate, methyl methacrylate, glycidyl methacrylate, divinyl, isoprene, vinylbenzene or undecylenic acid or the maleic anhydride, or polyethers, urethane.
3. prepare the method for the high inflexible polyvinyl chloride/inorganic rigid particle composite resin of high-impact, it is characterized in that, comprise the steps:
Organized inorganic rigid particles and vinylchlorid that said surface is had with the flexible polymer layer of chemical bond form bonding adopt suspension polymerization to carry out polymerization, and the weight percent of the various raw materials that adopted is:
Organized inorganic rigid particles 1～30wt%
Vinylchlorid 10～60wt%
Deionized water 30～80wt%
Dispersion agent 0.01～5wt%
Initiator 0.05～5wt%
Buffer reagent 0.05～5wt%
Complexing agent 0.01～5wt%
Chain-transfer agent 0.01～5wt%
Terminator 0.01～5wt%;
Said organized inorganic rigid particles is that claim 1 or 2 surfaces of being addressed have the organized inorganic rigid particles with the flexible polymer layer of chemical bond form bonding.
4. method according to claim 3 is characterized in that, comprises the steps:
Stirred 0.1～2 hour said organized inorganic rigid particles, vinylchlorid, deionized water, dispersion agent, initiator, buffer reagent, complexing agent and chain-transfer agent are cold, being warmed up to 40～80 ℃ is polymerized to pressure and drops to 0.2～1.0MPa, add terminator, adopt conventional method from reaction product, to collect high tenacity, high rush-resistant polyvinyl chloride/inorganic rigid particle composite resin then.
5. method according to claim 3, it is characterized in that said dispersion agent is selected from least a in methylhydroxypropylcellulose, hydroxypropylcellulose, polyvinyl alcohol, Polyvinylpyrolidone (PVP), polyethylene oxide fatty acid ester, the ethoxylation polyoxypropylene;
Said initiator is selected from 2, the 2-Diisopropyl azodicarboxylate, 2, the 2-2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), peroxy dicarbonate two (4-tertiary butyl cyclohexyl), di-cyclohexylperoxy dicarbonate, peroxy dicarbonate two (2-ethylhexyl), the two cardamom esters of peroxy dicarbonate, the peroxy dicarbonate di-n-propyl ester, di-isopropyl peroxydicarbonate, peroxy dicarbonate two-2-ethyl phenoxy, the peroxy dicarbonate diisobutyl ester, the two butyl esters of peroxy dicarbonate, the two cetyl of peroxy dicarbonate, peroxidation two (3,5, the own ester of 5-trimethylammonium), peroxidation PIVALIC ACID CRUDE (25) tert-pentyl ester, the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester, peroxidation neodecanoic acid-2,4,4-trimethylammonium pentyl ester, peroxidation neodecanoic acid isopropyl benzene ester, the special butyl ester of peroxidation neodecanoic acid, new peroxide tert-butyl caprate, peroxidation neodecanoic acid-3-hydroxyl-1,1-dimethyl butyl ester, peroxidation neodecanoic acid-1,1,3,3-tetramethyl-butyl ester, the new enanthic acid of peroxidation-3-hydroxyl-1,1-dimethyl butyl ester, the new enanthic acid tert-pentyl ester of peroxidation, the new enanthic acid tert-butyl ester of peroxidation, the new enanthic acid isopropyl benzene of peroxidation ester, the new enanthic acid tert-pentyl ester of peroxidation, peroxidation trimethylacetic acid isopropyl benzene ester, diisobutyryl peroxide, acetyl peroxide cyclohexyl sulfonic acid, peroxidation two different nonanoyls, dilauroyl peroxide, didecanoyl peroxide, peroxidation-2 ethyl hexanoic acid-3-hydroxyl-1,1-dimethyl butyl ester, 2, two (peroxidation of 2-ethyl hexanoyl)-2 of 5-, the 5-dimethylhexane, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidation-2 ethyl hexanoic acid tert-pentyl ester, tertbutyl peroxide, in the dibenzoyl peroxide one or more;
Said buffer reagent is selected from a kind of in sodium bicarbonate, saleratus, bicarbonate of ammonia, Trisodium Citrate, ammoniacal liquor, Sodium phosphate dibasic, the dipotassium hydrogen phosphate;
Said complexing agent is selected from EDTA disodium salt, EDTA sodium calcium salt, Sodium Nitrite or trisodium citrate;
Said chain-transfer agent is selected from carbon tetrabromide, bromo-trichloromethane, tetracol phenixin, 2 cbloropropane isopropyl chloride, chloroform, ethylene dichloride, methylene dichloride, monochloroethane, 1,1,2,2-tetrachloroethane, 2,4-dichloropentane, trieline, 2,4, a kind of in 6-three chloroheptanes;
Said terminator is selected from tetrachlorobenzoquinone, para benzoquinone, anthraquinone, p-ten.-butylcatechol, 2,5-two tert-pentyl Resorcinol, biphenyl is to amine, Resorcinol, dihydroxyphenyl propane, Meta-dinitrobenzene, 2, the 4-dinitrobenzene, 1,3, the 5-trinitrobenzene, the N nitrosodiphenylamine, nitrosobenzene, nitroso-, monomethylaniline, sulphur fork pentanoic, dithio dibenzoyl disulfide thing, the acetone semicarbazone thiocarbamide, 1,1-phenylbenzene-2-cumyl hydrazine, 2,2,6,6-tetramethyl--4-hydroxy piperidine nitroxyl free radical, iron trichloride, titanous chloride, a kind of in cupric chloride or the sulphur.
6. method according to claim 3, it is characterized in that, the preparation method that said surface has with the organized inorganic rigid particles of the flexible polymer layer of chemical bond form bonding comprises the steps: inorganic rigid particle is dispersed in the deionized water, dropping is with 5～25wt% coupling agent, fully reaction is 0.1～5 hour, be warmed up to 60～90 ℃, drip 1～15wt% emulsifier aqueous solution, continue to stir 0.1～3 hour, divide two-way to drip the aqueous solution that 30～200wt% contains double bond monomer and 0.05～3wt% letex polymerization initiator and 1～15wt% emulsifier mixture then, drip off in 1～2 hour, 60～90 ℃ were reacted 0.5～5 hour, divide two-way to drip the aqueous solution that 30～200wt% contains double bond monomer and 0.05～3wt% initiator and 1～15wt% emulsifier mixture again, drip off in 1～2 hour, 60～90 ℃ were reacted 1～5 hour, added 0.05～1wt% letex polymerization initiator solution, continued reaction 0.5～2 hour;
The raw material that adds in the reaction process is a benchmark with the weight of inorganic rigid particle all.
7. method according to claim 3, it is characterized in that, the preparation method that said surface has with the organized inorganic rigid particles of the flexible polymer layer of chemical bond form bonding comprises the steps: 0.1～5wt% coupling agent and inorganic rigid particle were disperseed in high-speed mixer 0.1～1 hour, add solvent then, stirred 0.1～1 hour, be warmed up to 60～90 ℃, drip 30～200wt% and contain double bond monomer and 0.05～3wt% polymerization starter, dripped off in 1～2 hour, continue reaction 1～6 hour, from reaction product, collect the organized inorganic particle then;
The solvent of being addressed is selected from least a in vinyl acetic monomer, N-BUTYL ACETATE, benzene, toluene or the dimethylbenzene;
The raw material that adds in the reaction process is a benchmark with the weight of inorganic rigid particle all.
8. according to claim 6 or 7 described methods, it is characterized in that the coupling agent of being addressed is selected from organic acid, silane coupling agent, titanate coupling agent, phosphate coupling agent or the aluminate coupling agent that has unsaturated double-bond.
9. method according to claim 8 is characterized in that, the organic acid that has unsaturated double-bond is selected from vinylformic acid, methacrylic acid or toxilic acid or its homopolymer and multipolymer;
Silane coupling agent is selected from vinyltrimethoxy silane, vinyltriethoxysilane, γ-chloropropyl trichloro-silane, γ-r-chloropropyl trimethoxyl silane, γ-chloropropyl triethoxysilane, γ-methacryloxypropyl trimethoxy silane, Alpha-Methyl acryloxy Union carbide A-162 or trimethylene isocyanate group Trimethoxy silane, trimethylene isocyanate group triethoxyl silane;
Titanate coupling agent is selected from sec.-propyl three oleoyl titanic acid ester, sec.-propyl triacryl titanic acid ester, sec.-propyl two (dodecyl tetradecyl) methacryloyl titanic acid ester, sec.-propyl dodecyl tetradecyl methacryloyl titanic acid ester, sec.-propyl distearyl ylmethyl acryl ester titanic acid ester, sec.-propyl dimethyl allene acidic group isostearoyl base titanic acid ester, sec.-propyl trimethylammonium acryl titanic acid ester, sec.-propyl two isostearoyl base acryl titanic acid ester, isopropyl stearyl-two acryl titanic acid ester, sec.-propyl triacryl titanic acid ester, isostearoyl ylmethyl acryl oxo ethanoyl titanic acid ester, two (methacryloyl) methyl oxyacetate titanate coupling agent, dimethyl propylene enoyl-oxo ethanoyl titanic acid ester, two acryl oxo ethanoyl titanic acid ester, methacryloyl isostearoyl base ethylene two oxy titanic acid ester, dimethyl propylene enoyl-ethylene two oxy titanic acid ester or two acryl ethylene oxide,1,2-epoxyethane base titanic acid ester;
Phosphate coupling agent is selected from four (2,2 two allyl oxygen methyl isophthalic acid-butenyls) two (2-three decyl phosphorous acid ester groups) titanic acid ester, methacrylic acid diethoxy phosphate coupling agent;
Aluminate coupling agent is selected from two (oleic acid Diethylene Glycol ester group) aluminic acid isopropyl ester, two allyl oxygen methyl phosphorodithioates close aluminium;
The emulsifying agent of addressing is selected from sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, alkyl oxy DAADBSA disodium, dodecyl alcohol sodium sulfate, sodium lauryl sulphate, ammonium lauryl sulfate, 2-second sodium hexy1 sulfate, tridecyl sodium sulfate, ethoxylated alkyl ether ammonium sulfate, straight chain ethoxylated alkyl ether ammonium sulfate, the alkyl oxide sodium sulfosuccinate, phenolic group ether sulfosuccinic acid in ninth of the ten Heavenly Stems sodium, ethoxylated alkylphenol ammonium sulfate, at least a in the cetyl trimethylammonium bromide;
The letex polymerization initiator of being addressed is selected from ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide, tertbutyl peroxide, isopropyl phenyl hydrogen peroxide, cumyl hydroperoxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, 4, a kind of in 4 '-azo two-(the 4-cyanopentanoic acid).
10. method according to claim 3 is characterized in that the preparation method of organized inorganic rigid particles comprises the steps:
The coupling agent that 5～100wt% is contained long flexible chain adds inorganic rigid particle, and blending dispersion is 0.1～1 hour in high-speed mixer;
The weight of the raw material inorganic rigid particle that adds in the reaction process is benchmark;
The coupling agent of being addressed that contains long flexible chain is selected from butyl polyacrylate base Trimethoxy silane; polyethylene oxide base Trimethoxy silane; poly(propylene oxide) base Trimethoxy silane; ethylene oxide type polyurethane-base Trimethoxy silane; propylene oxide type polyurethane base Trimethoxy silane; butyl polyacrylate ethyl triethoxy silicane alkane; polyethylene oxide ethyl triethoxy silicane alkane; poly(propylene oxide) ethyl triethoxy silicane alkane; ethylene oxide type polyurethane-base triethoxyl silane; propylene oxide type polyurethane ethyl triethoxy silicane alkane; butyl polyacrylate base dipyrophosphoric acid ester acyl group oxyacetate titanate; polyethylene oxide base dipyrophosphoric acid ester acyl group oxyacetate titanate; poly(propylene oxide) base dipyrophosphoric acid ester acyl group oxyacetate titanate; ethylene oxide type polyurethane-base dipyrophosphoric acid ester acyl group oxyacetate titanate; propylene oxide type polyurethane base dipyrophosphoric acid ester acyl group oxyacetate titanate; butyl polyacrylate base pyrophosphate acyl group oxo ethanoyl titanic acid ester; polyethylene oxide base pyrophosphate acyl group oxo ethanoyl titanic acid ester; poly(propylene oxide) base pyrophosphate acyl group oxo ethanoyl titanic acid ester; butyl polyacrylate base pyrophosphate acyl group oxo ethanoyl titanic acid ester; polyethylene oxide base pyrophosphate acyl group oxo ethanoyl titanic acid ester; poly(propylene oxide) base pyrophosphate acyl group oxo ethanoyl titanic acid ester; ethylene oxide type polyurethane-base pyrophosphate acyl group oxo ethanoyl titanic acid ester; propylene oxide type polyurethane base pyrophosphate acyl group oxo ethanoyl titanic acid ester; butyl polyacrylate two (2-three decyl phosphorous acid ester groups) titanic acid ester; polyethylene oxide two (2-three decyl phosphorous acid ester groups) titanic acid ester; poly(propylene oxide) two (2-three decyl phosphorous acid ester groups) titanic acid ester; ethylene oxide type polyurethane-base two (2-three decyl phosphorous acid ester groups) titanic acid ester; propylene oxide type polyurethane base two (2-three decyl phosphorous acid ester groups) titanic acid ester; propylene dimer acid butyl ester base pyrophosphate acyl group oxo ethanoyl titanic acid ester; dimerization Oxyranyle pyrophosphate acyl group oxo ethanoyl titanic acid ester; two poly(propylene oxide) base pyrophosphate acyl group oxo ethanoyl titanic acid ester; diepoxide for example type polyurethane base pyrophosphate acyl group oxo ethanoyl titanic acid ester; diepoxy propane type polyurethane base pyrophosphate acyl group oxo ethanoyl titanic acid ester; propylene dimer acid butyl ester phosphoric acid ester is closed aluminium; two polyethylene oxide phosphoric acid ester are closed aluminium; two poly(propylene oxide) phosphoric acid ester are closed aluminium; diepoxide for example type polyurethane phosphoric acid ester is closed aluminium; diepoxy propane type polyurethane phosphoric acid ester is closed aluminium; propylene dimer acid butyl ester base aluminic acid isopropyl ester; dimerization Oxyranyle aluminic acid isopropyl ester; two poly(propylene oxide) base aluminic acid isopropyl esters; a kind of in diepoxide for example type polyurethane base aluminic acid isopropyl ester or the diepoxy propane type polyurethane base aluminic acid isopropyl ester.
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