CN102276764A - Chemical modification method of polymer powder - Google Patents
Chemical modification method of polymer powder Download PDFInfo
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- CN102276764A CN102276764A CN 201110161926 CN201110161926A CN102276764A CN 102276764 A CN102276764 A CN 102276764A CN 201110161926 CN201110161926 CN 201110161926 CN 201110161926 A CN201110161926 A CN 201110161926A CN 102276764 A CN102276764 A CN 102276764A
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- Prior art keywords
- polymer
- solid particles
- coupling agent
- polymer solid
- surface modification
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- 229920000642 polymer Polymers 0.000 title claims abstract description 174
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000000843 powder Substances 0.000 title abstract description 102
- 238000007385 chemical modification Methods 0.000 title description 8
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- 239000007787 solid Substances 0.000 claims abstract description 53
- 230000004048 modification Effects 0.000 claims abstract description 49
- 238000012986 modification Methods 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000000126 substance Substances 0.000 claims abstract description 41
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- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 23
- 125000000524 functional group Chemical group 0.000 claims abstract description 15
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
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- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 150000002681 magnesium compounds Chemical class 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- 230000005012 migration Effects 0.000 description 1
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- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- IZGYIFFQBZWOLJ-CKAACLRMSA-N phaseic acid Chemical compound C1C(=O)C[C@@]2(C)OC[C@]1(C)[C@@]2(O)C=CC(/C)=C\C(O)=O IZGYIFFQBZWOLJ-CKAACLRMSA-N 0.000 description 1
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- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention discloses polymer powder subjected to surface chemical grafting modification. In the polymer powder, a reactive alkoxy silane group is chemically linked to the surface of polymer powder particles, the average grain diameter of the solid particles is between 5 microns and 800 microns, and the C/Si atom proportion on the surface of the polymer particles, measured by an X-ray photoelectron spectroscopy (XPS), is 100:(6-30). The invention also discloses a preparation method of the surface modified polymer solid particles, and the method comprises microwave promoted hydrolytic condensation of a specific functional group-containing silane coupling agent in a solvent-diluted hydrochloric acid system and grafting reaction of the specific functional group to the polymer chain under microwave promotion, wherein the hydrolytic condensation of the silane coupling agent and the microwave effect can be used for improving the grafting efficiency of the surface of the polymer powder particles. The modified polymer powder prepared according to the technology provided by the invention is applied to a cement mortar system, and the impact toughness of curing concrete can be remarkably improved.
Description
Technical field
The present invention relates to a kind of technology of polymer beads being carried out chemical modification, at polymkeric substance solid particles surface grafting organoalkoxysilane coupling agent, and adopt microwave assisting method to promote this out-phase graft reaction, promptly promote means by microwave, the high efficiency silane coupling agent chemical bond-linking of specific reactive functionality that will contain is to the molecular chain on polymer solid particles surface, obtain the surface and be rich in the polymer solid particles of alkoxysilane groups, make it have the surface chemical reaction function.Belong to the polymer modification category, the potential fields such as coating, printing ink, tackiness agent, organic/inorganic composite material that are applied to.Innovation part of the present invention is that method and microwave-assisted that the polymkeric substance solid particles is silicane coupling agent surface grafted promote this solid phase grafting reaction.
Background technology
Matrix material is by two or more materials with different properties, by the method for physics or chemistry, forms the material with new capability on macroscopic view.Various materials make up for each other's deficiencies and learn from each other on performance, produce synergistic effect, make the over-all properties of matrix material be better than former composition material and satisfy various requirement.The body material of matrix material is divided into metal and nonmetal two big classes.Nonmetal basal body mainly contains synthetic resins, rubber, pottery, graphite, carbon etc.Strongthener mainly contains glass fibre, carbon fiber, boron fibre, aramid fiber, silicon carbide fiber, fibrous magnesium silicate, whisker, wire and hard particulates etc.The matrix material of macromolecule matrix is to use a comparatively extensive and important class, comprises macromolecule-inorganic mineral composite, polymer-broad varietys such as all kinds of fibre composites.Polymer-based composite is external phase usually with the high molecular component, forms macroscopic view with the out-phase material mixing and sees the form that is separated of phase region size to being situated between.Polymer composite is wherein to use a comparatively extensive and important class, the material that polymer composite is processed by matrix resin, strongthener (filler, glass fibre), functional aid process particular devices such as (coupling agent, releasing agent, toughner) usually mainly contains unsaturated polyester composite, phenolaldehyde moulding compound, epoxy plastic cement, PGL, epoxy casting material, epoxy glass fiber cloth etc.Its general characteristics are: high strength, high electrical performance, good moldability etc.Specific to the cement concrete material that the present invention paid close attention to, common cement concrete has high strength, high impact properties characteristics, but the shock resistance flexibility is generally relatively poor, particularly when standing the impact of shaking property, because cement concrete lacks the stress dissipation characteristic of flexible structure, its vibration resistance is relatively poor usually; And concrete ftractures by stress in a single day, and crackle will enlarge rapidly, until the concrete structure fragmentation.In cement concrete prescription, add flexible polymer dispersed phase, often can improve the concrete material toughness, improve material, suppress the diffusion of cement block crackle, improve cement product work-ing life in frequent vibration environmental applications performance.This also is the technological development direction in current cement concrete material field, and adds the research and development of modified cement-concrete based on waste-tyre rubber-powder.Organosilicon crylic acid latex in addition, emulsification rubber powder have become widespread use in cement material, but because of polymkeric substance itself contains carboxyl, siloxane groups, stronger with the interface interaction of silicate cement and sand grains, usually can obtain application performance such as waterproof, shock resistance preferably.But this base polymer material is via the synthetic gained of monomer, and cost is higher, and addition is had relatively high expectations.
Polymer powder material and cement concrete blend being made polymer-cementitious composite concrete, form the compound system that mixes of polymer phase and silicic acid salt face, is a kind of concrete high-performance technique direction comparatively directly and cheaply.Exist character to differ bigger out-phase contact surface between the polymer composite different matrix, promptly so-called interface.In the cement concrete system that tire glue powder is filled, the junked tire material of main part is styrene-butadiene rubber(SBR) and sooty mixture, contain the part fortifying fibre in addition, not surface treated tire glue powder has than low surface energy, consistency extreme difference with the wetting ability silicates basal body, simple filling can only cause all mechanical properties generally to reduce, and can't play and improve the concrete performance effect.At present comparatively elementary at modification before the blend of tire glue powder, general employing sodium hydroxide solution simply immersing, washing, or simply coat rubber powder with organic acid, silane coupling agent, though can effectively improve the concrete snappiness, but the toughness raising also has only 20 ~ 40%, and bigger to concrete crushing strength and folding strength infringement, polymer powder adds makes ultimate compression strength and folding strength reduce above more than 70%.And polymer powder adds part by weight can not surpass 15%, little to the contribution that concrete proportion reduces.For a change this disadvantage based on the basic volume method of conventional inorganic fillers surface modification, can be attempted design and adopt the coupling agent method, the coupling agent that will have the two poles of the earth characteristic is as the bridge chain, act on macromolecule matrix and inorganic blend components respectively, composite material interface intensity is increased, improve over-all properties.Therefore, coupling agent is to make a crucial class functional aid in the composite material.
Coupling agent is the material that a class has two different properties functional groups, a part of functional group in their molecules can with reactive organic molecule, another part functional group can with the reaction of the planar water on inorganics surface, form firm bonding.The effect of coupling agent in matrix material be it can with some radical reaction on strongthener surface, can react with matrix resin again, between strongthener and resin matrix, form an interfacial layer, interfacial layer can transmit stress, thereby strengthened bond strength between strongthener and the resin, improved performance of composites, can also prevent simultaneously not with other medium to contacting permeation, improve interfacial state, helped ageing-resistant, the proof stress and the electrical insulation capability of goods.
Chemical structure and composition by coupling agent are divided into organic chromium complex compound, silicane, titanate ester and aluminic acid compound four big classes, in addition, also have some group coupling agents, comprise zirconium ester coupling agent and magnesium compound coupling agent etc.Wherein, be easier to Balance Treatment between silane coupling agent reactive behavior and the stability in storage, the structure of silane coupling agent, functional group, kind are also very abundant, and cost is relatively low, and toxicity is little, transform thorough, residual low easily.Thereby silane coupling agent is a class coupling agent that is most widely used.
Generally include siliceous hydrolysable group and reactive organo-functional group on the silane coupling agent structure, available general formula Y (CH
2)
nSiX
3Expression, wherein, n=0-3; X represents hydrolyzable group; Y is reactive organo-functional group, can react with polymkeric substance or polymerization single polymerization monomer.X is chloro, methoxyl group, oxyethyl group, methoxy ethoxy, acetoxyl group etc. normally, generates silanol (CH during these group hydrolysis
2-Si (OH)
3), and combine with inorganic substance, form siloxanes.Y is vinyl, amino, epoxy group(ing), methacryloxy, sulfydryl, azido-or urea groups etc.These reactive groups can combine with the organic substance reaction.Therefore,, can between the interface of inorganic substance and organic substance, erect " molecule bridge ", the material of two kinds of character great disparities is linked together improve the effect of performance of composites and increase bonding strength by using silane coupling agent.This characteristic of silane coupling agent is applied on the glass filament reinforced plastics (glass reinforced plastic) the earliest, make the surface treatment agent of glass fibre, mechanical property, electric property and the ageing resistance of glass reinforced plastic are greatly improved, and the importance in frp industry gains public acceptance already.
The purposes of silane coupling agent expands the fiberglass surface treating agent of fibreglass reinforced thermoplastic (FRTP) usefulness, surface treatment agent and sealing agent, resin concrete, water crosslinking property polyethylene, resin package material, shell mouding, tire, band, coating, tackiness agent, abrasive substance (grinding stone) and other the surface treatment agent of inorganic filler to from glass filament reinforced plastics (FRP).In the group of this two classes performance inequality of silane coupling agent, most important with Y group, it is very big to product properties influence, works the performance effect that determines coupling agent.Have only resin to react, the intensity of matrix material is improved when Y group energy and correspondence.The general requirement Y group will and can play linked reaction with resin compatible.
The using method of relevant silane coupling agent is comparatively ripe, and the simplest method is that suitable silane coupling agent is directly added in the recipe ingredient, relies on diffusive migration, and coupling agent is attached to inorganic material surface, and concurrent looks is answered the interface keying action.Secondly, also silane coupling agent can be dissolved in the appropriate solvent, inorganic material surface is anticipated, coupling agent is riveting in inorganic material surface, mix with macromolecular material again, the coupling agent organo-functional group of inorganic material surface and polymer-based carbon precursor reactant, the polymer composite of formation interface mortise.In addition as a kind of technological method not too widely, also can synthesize or the modification stage at polymkeric substance, silane coupling agent is incorporated on the soluble polymer chain, as the silicon propylene copolymer in building coating field etc., polymkeric substance connects effect itself that play binding agent, is beneficial to film forming, simultaneously, the interface can take place and combine in the alkoxysilane groups of polymer lateral chain with the mineral filler in the formulation for coating material, strengthen the over-all properties of coating.
In general, coupling agent application mode the most widely still is conceived to the modification of coupling agent to metal, material surface such as inorganic, improve the interface bond strength of these materials and macromolecular material, and initiatively organic polymer material is carried out surface modification with coupling agent, the research that is applied to polymkeric substance-concrete system then is comparatively rare.In existing bibliographical information, the technology comparatively approaching with the present invention is that polymeric powder is made an addition to the sand-cement slurry system, expectation improves concrete flexibility or elasticity, its process procedure has also used silane coupling agent to carry out surface treatment to reclaiming the rubber tyre powder, but only limiting to coupling agent applies in the simple physical of vulcanized rubber powder, do not relate to surface chemical modification, the performance of its gained concrete material should also have greater room for improvement.As for the extensive latex powder adding technique that adopts of concrete field, be based on latex powder part emulsification in the sand-cement slurry system, the mortar particle is formed interface interaction, improve concrete intensity and closely knit water-repellancy, this latex powder itself derives from emulsion system, in mortar, be partly dissolved emulsification, also do not relate to silane coupling agent the polymer beads process for modifying surface.
Summary of the invention
As previously mentioned, traditional mode is that the polymkeric substance of dissolved state is mutually compound with surface-treated inorganic materials, and row solidify to form the matrix material with certain performance again.Perhaps raw materials such as monomer are mixed with inorganic materials, the crosslinking curing of going again forms the high score matrix material.Its essential characteristic is to be in dissolved state in order to the high molecular component of making matrix material when mixing with inorganic materials, and after formation met the material crosslinking curing, polymeric constituent often can the external phase form occur, the parcel inorganic materials.The generation type of polymer composite is also in continuous development, be different from the complex method of above-mentioned soluble polymer, use indissoluble or insoluble polymer powder to make polymer composites and become new developing direction, comprise this insoluble polymer pulverized structure in the composite system, help to improve the mechanical property of matrix material, and the viscosity of system will reduce greatly in the prescription production process, be beneficial to machine-shaping.For example the vinyl polymer powder of polymer cement field appearance makes an addition in the mortar, the concrete material that solidifies formation is the most outstanding at aspects such as shock resistance, water-repellancy, dynamic stress emergent properties, forms the high performance material industry direction of a novelty gradually.In addition, with indissoluble or insoluble polymer powder and aqueous resin and be used for making composite polymer-inorganic matter material, can obtain more excellent performance, provide successive bonding phase behind the aqueous resin solidification, indissoluble or insoluble polymer fine particle are as organic filling phase, the stress-strain pooling feature is provided, and has certain plasticity or elasticity, give matrix material comprehensive excellent performance jointly.
Yet, as the polymer powder of disperse phase with inorganic materials compound tenses such as silicate, granulous polymkeric substance and inorganic materials interface interaction generally a little less than, mechanics of materials intensity is not high.Therefore, the polymer powder particle surface is carried out chemical modification and just seem very necessary to adapt to this class purposes.The technology of the present invention is exactly to utilize commercially available multiple polymers powder directly to carry out modification, a certain amount of alkoxysilane groups of bonding in powder particle surface or shallow surface structure, this modified particle is when mixing with inorganic materials, can be by alkoxysilane groups hydrolysis, the condensation reaction of polymer beads sub-surface, polymer particle closely is connected with inorganic materials, reaches the purpose that improves the strength of materials.In addition, polymer powder after this modification is because high efficiency surface reaction, also can add in the aqueous polymer formulators system, start the reaction of particle surface alkoxysilane groups under proper condition, aqueous polymkeric substance and polymer particle are coupled together, realize crosslinking curing, the actual effect of serving as the powder linking agent of polymer-modified powder of this moment.So the formed product of the technology of the present invention will have comparatively wide application field, will have higher using value in fields such as cement-base composite material, compound sizing agent, compound thick coating, terrace paint.
The conventional composite materials technology generally is the surface preparation at the inorganic materials component, manages to form the coupling agent molecule layer at inorganic material surface, and then realizes the mortise at polymkeric substance-inorganic materials interface.Indivedual technical literatures have also been reported improved chemicals such as organic polymer powdered material surface-coated silane coupling agent such as rubber, improve the interface bond strength of polymeric powder particle and inorganic matrix material, but the simple physical that also only limits to the polymeric powder particle surface coats, do not form Chemical bond between properties-correcting agent and the polymeric particles, it is barely satisfactory that the multi phase interface after material is compound improves effect.Innovation part of the present invention is indissoluble or insoluble polymer powder surface are carried out chemical modification in advance, form a certain amount of alkoxysilane groups in the polymer beads sub-surface, strengthen the interface interaction intensity of polymer particle and inorganic materials, improve material property.Secondly, the technology of the present invention adopts microwave to promote the graft reaction of the solid shape particle surface of polymkeric substance.Moreover the technology of the present invention is based on indissoluble or does not allow the surface modification reaction of polymer particle, and the design that is different from the alkoxysilane-modified polymkeric substance of aqueous in the past solubility is synthetic.The technology of the present invention is based on ripe basic reactions such as ester bond aminolysis, the replacement of halo hydroxylamine, sulfydryl-two key additions, nitrine activation insertion reaction, and the invention technology has perfect the principles of science rationally, improves more remarkable to the impelling strength of cement concrete system.
According to the first embodiment of the present invention, the polymer solid particles of surface modification is provided, wherein introduced the alkoxysilane groups that can react on this polymer beads surface or in the shallow top layer, the mean particle size of this solid particulate is 0.5 micron～2000 microns, the C/Si atomic ratio that is recorded the polymer beads surface by x-ray photoelectron spectroscopy (XPS) is 100: 6-30, polysiloxane or polysiloxane copolymer are got rid of or do not comprised to this polymkeric substance.
Preferably, the mean particle size of this solid particulate is the 5-800 micron, and the C/Si atomic ratio that is recorded the polymer beads surface by x-ray photoelectron spectroscopy (XPS) is 100: 9-26, more preferably 100: 12-20, more preferably 100: 13-18.
Generally speaking, polymkeric substance in the polymer solid particles of this surface modification is selected from (methyl) Voncoat R 3310 or its multipolymer, ryuron or its multipolymer, leifa, polyethylene-vinyl acetate copolymer; one or both in the styrene-butadiene rubber(SBR) or multiple, and this polymkeric substance also comprises the matrix material based on these polymer materialss and carbon black or other mineral filler formation.
Generally, the above-mentioned alkoxysilane groups that reacts be keyed on the surface of polymer solid particles via functional group or polymer molecule or polymer chain in the shallow top layer on.According to the XPS test feature, its depth of material that can effectively survey be the following 2 nanometer degree of depth of material surface, i.e. the alleged polymer beads surface and the degree of depth on shallow top layer in this specification sheets.
The alkoxysilane groups that can react comprises Trimethoxy silane base, triethoxysilicane alkyl, and their partial hydrolysis condensed forms, they be connected on the surface of above-mentioned polymer solid particles by chemical bond-linking or polymer molecule or polymer chain in the shallow top layer on.Generally, the alkoxysilane groups that can react is selected from Trimethoxy silane base (CH
3O)
3Si-R-, triethoxysilicane alkyl (CH
3CH
2O)
3Si-R-, and their incomplete hydrolytic condensation form, wherein-the R-group includes but not limited to-CH
2-,-CH
2CH
2-or-CH
2CH
2CH
2-.
Second embodiment according to the present invention, the method of the polymer solid particles for preparing above-mentioned surface modification is provided, it is on 5 microns～800 microns the surface of polymer solid particles raw material or in the shallow top layer that this method is included in mean particle size as starting raw material, by molecule interchain reaction on the amino on the silane coupling agent, sulfydryl, bisthioether linkage, azido-and the polymer beads, introduce alkoxysilane groups through chemical bond-linking on the polymer solid particles surface.This surface modification reaction preferably by means of microwave be used for carry out, promptly belong to microwave-assisted reaction.With respect to common thermal response, the reaction of the polymer solid particles interface crosslinking of microwave-assisted will be carried out with higher efficient.
Generally, the profile of polymer solid particles raw material is regular spherical or irregular form, and it generally is not dissolve in organic solvent or soluble organic polymer particles in the specified solvent of minority only.
Polymer solid particles as raw material is selected from (methyl) Voncoat R 3310 or multipolymer, leifa, vinyl-vinyl acetate copolymer, one or both in the middle of ryuron or the multipolymer, the particle of styrene-butadiene rubber(SBR) or multiple.These polymkeric substance or multipolymer are crosslinked or uncrosslinked, and these polymkeric substance or multipolymer also can reclaim the field from waste and old material, contain carbon black or other mineral fillers." micro mist ", " particle " or " particulate " can exchange use each other in this application.In the art, (methyl) acrylate comprises acrylate and/or methacrylic ester.
According to the present invention, polymer solid particles surface alkoxysilane groups is from the interfacial chemical reaction of polymer solid particles and silane coupling agent, this silane coupling agent is meant except that having Trimethoxy silane base or triethoxysilicane alkyl, also must have a kind of in primary amine groups, secondary amine, sulfydryl, bisthioether linkage, polythiaether key, the azido-or have primary amine groups and secondary amine simultaneously.Be that the present invention preferably uses and contains the trialkoxy silane coupling agent that is selected from one or both groups in primary amine groups, secondary amine, sulfydryl, bisthioether linkage, polythiaether key, the azido-.This silane coupling agent can have primary amine groups and secondary amine simultaneously.
Preferably, as silane coupling agent, the present invention uses and contains amino organoalkoxysilane coupling agent (for example amine alkylalkoxy silane coupling agent, or polyamino silane coupling agent); Mercaptosilane coupling agents and multi-sulfur silane coupling agent; Or azido-silane coupling agent.
The condition of this microwave-assisted reaction is the microwave power of 400-9000 watt of per 1 kg of polymer solid particulate raw material configuration, and the microwave generator operating frequency is about 2400-2500 MHz, and the modified-reaction time under the microwave-assisted is 8-30 minute.
Polymer solid particles surface chemical modification reaction conditions is the polymer solid particles suspended dispersed to be carried out microwave exposure carry out modification in the solution that is dissolved with described silane coupling agent.Generally, the mass ratio that feeds intake of polymer solid particles and silane coupling agent of the present invention is 100:5-30, and preferably 100:8-25 is more preferably 100:12-20.For the solvent in being dissolved with the solution of silane coupling agent, require this solvent can dissolve silane coupling agent, but can the dissolve polymer solid particulate.These solvents comprise that boiling point is higher than 80 ℃ the alcohols with 3-15 carbon atom, ketone, ester class, ethers etc., comprising but be not limited to Virahol, propyl carbinol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, glycol-monoacetin, Diethylene Glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Diethylene Glycol monoacetate, propylene glycol, propylene glycol monomethyl ether, dihydroxypropane single-ether, butanone, pentanone or pimelinketone.
In the preferred case, in the reaction process of the surface modification of polymer beads, use 5-25wt% concentration (preferred 6-20wt%, more preferably 7-18wt%, more preferably 10-15wt% again) dilute inorganic acid solution is as catalyzer, promote silane coupling agent appropriateness hydrolytic condensation, require employed organic solvent to dissolve each other, form homogeneous phase solution with diluted mineral acid aqueous solution appropriateness.This just needs employed organic solvent to have certain wetting ability, can be single alcoholic solvent, also can adopt water-soluble solvent preferably and water-soluble relatively poor solvent to use.In addition, the reaction process of polymer solid particles surface modification is to contain the silane coupling agent of particular functional base and the graft reaction on polymer beads surface, and this requires our employed solvent system to be avoided reacting with the functional groups of silane coupling agent.Mineral acid as the catalyzer of silane coupling agent hydrolysis reaction in the process of surface modification is selected from hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid.
The stock polymer powder that the present invention is contained is meant that particle diameter is positioned at the solid shape polymer beads of the sight size that is situated between, have to utilize to be worth and be of a size of 5 microns-800 microns, but according to composition principle of the present invention, the polymer beads of other grain sizes also can promote technology by above-mentioned microwave, silicane coupling agent surface grafted at polymer beads, introduce alkoxysilane groups.Its mode of appearance can be the sphere of rule, also can be other irregular forms, comprises the particles dispersed form of local adhesion.Polymer powder can be crosslinked or the non-crosslinked particle, and the non-crosslinked particle is meant that generally model ylid bloom action power is stronger between those linear polymer molecular chains, the polymer beads that solvability is relatively poor; Cross-linking polymer particle comprises physical crosslinking and chemically crosslinked.Polymer powder then can obtain the insoluble polymer powder of chemically crosslinked as introduce the polyfunctional monomer copolymerization in manufacturing processed.The technology of the present invention does not relate to the manufacturing of polymer raw materials powder, but the part technology relates to the crosslinked reinforcement of the later stage of polymer powder, the present invention mainly carries out surface chemical modification with regard to obtainable part kind polymer powder on the market, gives higher use properties of this material and application widely.
Specifically, the polymer powder of indication of the present invention (also claiming particle) is that normal temperature is solid-state, easily the atomizing polymkeric substance and with the mixture of mineral filler, this base polymer includes but not limited to polymethylmethacrylate (PMMA), the polyacrylic acid isobornyl thiocyanoacetate, poly-(methyl) isopropyl acrylate, polymethyl acrylic acid-2-hydroxypropyl acrylate, the methyl methacrylate-butyl acrylate multipolymer, methyl methacrylate-butyl acrylate-styrol copolymer, polyvinyl acetate (PVA) (PVAc), vinyl acetate-ethylene copolymer (EVA), polyvinyl chloride (PVC), vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-copolymer-maleic anhydride; one or both in styrene-butadiene rubber(SBR) or the waste-tyre rubber-powder or multiple.All derive from ready-made large chemical materials in principle, need not customized specially.These polymeric powder particles structural particular functional group can utilize, and is designed to react with the silane coupling agent particular functional group, realizes the grafting of silane coupling agent on the polymer beads surface.
" surface modification " is used interchangeably with " (surface) graft reaction " in this application.
When the polymer solid particles that needs surface modification is (methyl) Voncoat R 3310 and copolymer powder particle (being solid particulate), the grafting of this polymkeric substance can utilize this polymer molecular chain side group ester bond and amino ammonolysis reaction, to contain amino silane coupling agent and be grafted to the polymeric powder particles surface, realize the modification of (methyl) acrylic ester polymer particle surface.Except the ammonolysis reaction of the simple single amino of amino silicane coupling agent to the polymer lateral chain ester group, the silane coupling agent that contains a plurality of amino (comprising primary amino and secondary amino group) can be by a plurality of amino and a plurality of contiguous ester group generation ammonolysis reactions of (methyl) acrylic ester polymer side chain, when introducing alkoxysilane group, also will improve crosslinked polymer density and intensity to the certain crosslinked action of polymer formation.In addition, when polymer beads being carried out microwave promotion graft reaction, contain diluted mineral acid (for example hydrochloric acid) in the solvent environment, microwave promotes down, the hydrolytic condensation of alkoxysilane groups can comparatively fast take place, formation contains the siloxanes oligomer of a plurality of alkoxysilane groups and a plurality of amino, this oligomer is because the amino functionality increase, probability to (methyl) acrylic ester polymer particle surface graft reaction increases, help improving the modification efficiency on polymer solid particles surface, increase alkoxysilane groups and silanol groups graft ratio on the polymeric powder particles surface.
The copolymer powder particle grafting of polyvinyl chloride and vinylchlorid is to utilize C-Cl bond structure abundant on the polymkeric substance, by the amino of silane coupling agent and the reaction of the C-Cl key on the polymer chain, alkoxysilane groups can be incorporated into the polymer solid particles surface.Equally also there is aforesaid polyamino response situation, improves crosslinked polymer, increase the grafting efficiency and the graft ratio on polymer beads surface.
When the polymer solid particles that needs surface modification is based on the powder particle of the homopolymer of vinyl-acetic ester and multipolymer, although also there is abundant acetic ester structure in polymer lateral chain, the alkoxysilane groups in the coupling agent can not be grafted on the polymer beads with the ammonolysis reaction of amino silicane coupling agent.
As for the polymeric powder particles of styrene-butadiene rubber(SBR) class, then more do not have and by above-mentioned ammonolysis reaction silane coupling agent to be linked on the polymer molecular chain, but be rich in carbon-carbon double bond on the butylbenzene rubber molecular chain.General knowledge based on silane coupling agent, we know that the silane coupling agent that contains sulfydryl can form and has the sulphur free radical of forcing into very much reactive behavior under the free radical effect, carbon-carbon double bond on the styrene-butadiene rubber(SBR) molecular chain is implemented high efficiency addition, and the alkoxysilane groups with silane coupling agent is anchored in the styrene butadiene rubber polymeric powder particle surface simultaneously.Required free radical can pass through to add a small amount of superoxide, and promotes accelerate decomposition with microwave, produces free radical.Superoxide can be selected from conventional superoxide, comprises benzoyl peroxide, peroxidation isobutyryl, dicumyl peroxide, dicumyl peroxide etc., and the consumption of superoxide is the 50-100%(weight ratio of silane coupling agent consumption).Remove the silane coupling agent that contains sulfydryl, the silane coupling agent that contains double thioether, four sulfide based structurals also can generate the sulphur radical structure under heating, microwave promotion or free radical effect, the polymkeric substance carbon-carbon double bond is carried out addition, introduces alkoxysilane groups.Equally as previously mentioned, the prehydrolysis condensation of silane coupling agent forms the siloxane oligomer of many sulfydryls, many alkoxysilane groups, and this all helps improving polymeric powder particles surface grafting efficient.
Ultimate principle based on the polymer chemistry reaction, also may exist multiple on the polymer chain for the reactive group that utilizes, to realize the polymer beads surface grafting, to the particular polymers powder particle, if contain acid anhydrides, epoxy group(ing), hydroxyl, carboxyl, amino isoreactivity group on the polymer chain, all can adopt corresponding silane coupling agent to carry out graft modification, obtain the polymeric powder particles of surperficial alkoxy silane group modification.Be that polymer surfaces microwave disclosed in this invention promotes that modification technology also is suitable for numerous polymer powder materials.
(carbon-carbon double bonds not on its polymer chain is difficult to use the sulfydryl coupling agent and the polythiaether coupling agent carries out surface graft modification to it) can select the silane coupling agent that contains azido-for use when the polymer solid particles that needs surface modification is based on the powder particle of the homopolymer of vinyl acetate monomer and multipolymer (being PVAc or EVA).Azido-be heated or UV-irradiation under be decomposed to form the nitrence free radical, more active c h bond has high efficiency insertion reaction activity on this radical pair polymer chain, this is confirmed in Essential Chemistry research repeatedly.Utilize this response characteristic, the silane coupling agent that contains azido-can be chemically bonded to comparatively inert polymeric powder particles surface such as EVA, PVAc, styrene-butadiene rubber(SBR), realize having the polymer solid particles surface modification of general applicability.Be that azido-coupling agent described here not only is applicable to above-mentioned EVA, PVAc, styrene-butadiene rubber(SBR), and be applicable to and be rich in c h bond, especially contain other all polymkeric substance of active c h bond.For EVA, PVAc, styrene-butadiene rubber(SBR), the insertion graft reaction technology of above-mentioned employing nitrine coupling agent all is suitable for.The nitrence free radical that azido-produces also shows stronger addition cyclization activity to the alkene carbon-carbon double bond, equally also can this alkoxysilane groups be grafted to the polymeric powder particles surface, this is particularly suitable to the polymer materials that styrene-butadiene rubber(SBR) etc. is rich in carbon-carbon double bond.In addition, the hydrolytic condensation of silane coupling agent under the dilute hydrochloric acid catalysis, formation has the siloxane oligomer of a plurality of azido-s and a plurality of alkoxysilane groups, these all will help increasing the graft modification efficient of polymer surfaces, and the multiple spot graft reaction of siloxane oligomer also will improve the cross-linking density of polymer beads.
Among the present invention for the modifying process on polymeric powder particles surface, might run into that polymer powder is partly dissolved or excessive swollen phenomenon in solvent, this all will influence the grafting of alkoxysilane groups on the polymer beads surface, cause polymkeric substance loss and surface grafting control undesirable.Carry out on the polymer beads surface with guarantee grafting chemical process for suppressing this situation, it is crosslinked in advance to adopt multifunctional linking agent that polymer beads is implemented, and improves the particle cross-linking density, reduces solubleness (strengthening anti-dissolubility).Alleged multifunctional linking agent is quadrol, diethylenetriamine or triethylene tetramine etc. preferably, and these linking agents are crosslinked effectively to (methyl) acrylic ester polymer particle and vinyl chloride-base polymer particulate.For the polymer beads of vinyl acetate monomer, can use oxalic dialdehyde, glutaraldehyde etc. is as linking agent, improves cross-linking density.When the polymer powder that is adopted or solid particulate are partly dissolved (solubleness is higher than 6%) or excessively during swelling (swelling ratio is greater than 10%), use multifunctional linking agent to implement crosslinked in advance to polymer beads before can taking place at the graft reaction of surface modification in solvent.Crosslinkedly in advance can improve the particle cross-linking density, reduce solubleness.
" choosing " expression wantonly exists or does not exist.
Concrete amine alkylalkoxy silane coupling agent (promptly containing amino organoalkoxysilane coupling agent) includes but not limited to 3-aminopropyltriethoxywerene werene (KH-550, the A-1100 of U.S. prestige section, Dow corning Z-6011, the Japan KBE-903 of SHIN-ETSU HANTOTAI), Degussa Dynasylan AMEO), 3-TSL 8330 (KH-540, the A-1110 of prestige section, DOW CORNING Z-6011, the Japan KBM-903 of SHIN-ETSU HANTOTAI, Degussa Dynasylan AMMO), the amino butyl triethoxyl silane of 4-, between-the aminophenyl Trimethoxy silane, right-the aminophenyl Trimethoxy silane, N-ethyl-3-trimethoxy silicon-2-methyl-propyl amine, N-methylamino-propyl trimethoxy silicane, N-(the aminoethyl)-3-aminopropyl trimethoxysilane (A-1120 of prestige section, KH-792, NQ-792, DOW CORNING Z-6020 ﹠amp; Z 6094, the Japan KBM-603 of SHIN-ETSU HANTOTAI, Degussa Dynasylan DAMO), N-(aminoethyl)-3-aminopropyl triethoxysilane, N-phenyl-γ-An Bingjisanjiayangjiguiwan coupling agent, the poly-aminoalkylsilane of aromatic base modification (Silquest A-1128 Silane), 3-aminopropyl three (methoxy ethoxy oxyethyl group) silane, the amino undecyl triethoxyl silane of 11-, between-the amino-benzene oxygen propyl trimethoxy silicane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane (dawn SG-Si602, the A-2120 of prestige section, the Japan KBM-602 of SHIN-ETSU HANTOTAI, Degussa Dynasylan 1411), 3-aminopropyl methyl dimethoxysilane, diethylenetriamine base propyl trimethoxy silicane (A-1130 of prestige section), N-[3-(trimethoxy is silica-based) propyl group] n-Butyl Amine 99, N-ethyl-3-Trimethoxy silane-2-methyl propylamine, N-phenylamino propyl trimethoxy silicane, N, N-pair-(triethoxysilylpropyl) imines (G-402), N, N-pair-(trimethoxy silicon propyl group) imines, two [3-(trimethoxy is silica-based) propyl group] quadrol etc.
When selecting for use the polyamino silane coupling agent that polymkeric substance is carried out surface modification, the polyamino reactive center also will cause the partial cross-linked of polymer powder surface to top layer.
Mercaptosilane coupling agents and multi-sulfur silane coupling agent include but not limited to gamma-mercaptopropyltriethoxysilane (KH-580, the A-1891 of prestige section, Degussa Dynasylan 3201), γ-mercaptopropyl trimethoxysilane (KH-590, the A-189 of prestige section, DOW CORNING Z-6062, the Japan KBM-803 of SHIN-ETSU HANTOTAI, Degussa Dynasylan MTMO), two-(the silica-based propyl group of γ-triethoxy) tetrasulfide (KH-845-4), two-(the silica-based propyl group of γ-triethoxy) tetrasulfide wax (dawn RSi-E, be that the KH-845-4 silane coupling agent is the mixture of carrier with wax), two (the silica-based propyl group of triethoxy) disulphide (dawn SG-Si996, the A-1589 of prestige section, DOW CORNING Z-6820, Degussa Si 75/Si 266)
The azido-silane coupling agent includes but not limited to γ-azido-propyl trimethoxy silicane, γ-azido-propyl-triethoxysilicane, 2-(4 '-azidophenyl) ethyl triethoxysilane, 2-(4 '-azidophenyl) ethyl trimethoxy silane, 3-(4 '-azidophenyl) propyl trimethoxy silicane, 3-(4 '-azidophenyl) propyl-triethoxysilicane.
The alleged microwave of the present invention promotes that the part by weight of stock polymer powder, organic solvent, dilute hydrochloric acid, silane coupling agent is 100: 10-200: 10-200: 5-30 in the modified-reaction.
The functionalized silane coupling agent belongs to the out-phase surface reaction to the graft reaction on polymer powder surface, can adopt ultrasonic technology to promote the out-phase surface reaction in the traditional method, reaction mixture is on the ultrasonic pretreatment basis, adoption of innovation microwave of the present invention promotes technology, improves the reaction of polymer particle surface grafting.Polymer powder surface grafting reaction under the microwave action approximately needs to continue 6-40 minute, and after-filtration, solvent wash, drying, sealed storage.Solvent for use in principle can recycle.
The surface modification polymer powder that all obtain in the present invention can characterize by means such as original position reflection absorption ftir spectroscopy, x-ray photoelectron spectroscopy (XPS), thermogravimetric analysiss.The technology of the present invention adopts ESCALAB 250 model x-ray photoelectron spectroscopy (U.S. THERMO VG company) and NETZSCH TG 209 F3 Tarsus type thermogravimetric analyzers (German Netzsch company) contrast to characterize.The bound energy fignal center of elements such as significant C, H, O appears in the XPS spectrum figure of pure polymer powder usually, behind the surface grafting alkoxysilane groups, its XPS collection of illustrative plates tangible alkoxyl group occurs and replaces environment Si element 2p electron binding energy fignal center near 102.4 eV, correspondence is hydrolyzable alkoxy TMOS structure not, shows that silane coupling agent is linked on the polymer powder.103.5 near the Si atom 2p transition of electron signal that occurs the eV shows the existing partial hydrolysis condensation of institute's alkoxysilane groups that connects, the existence of expression siloxane oligomer and silanol structure.According to XPS bound energy signal calculated by peak area, modification post polymerization thing powder surface C/Si atomic quantity ratio is about 100:6 ~ 100:30.Thermogravimetric analysis under the air ambient shows, the thermogravimetric curve basically identical before and after the polymer powder modification, and the residual heavy rate in the time of 600 ℃ is 0.2 ~ 0.6%, no significant difference, it is residual not detect significant silicon-dioxide.Comprehensive explanation alkoxysilane groups mainly grafts on the surface of polymeric powder particles, but not the polymer particle body, promptly after the graft modification, the polymeric powder particles surface local is covered by the siloxane structure bonding.
Description of drawings
Fig. 1 isThe impelling strength comparison diagram of composite product.
Embodiment
Embodiment 1:
100g polymethylmethacrylate (PMMA) the powder dispersed with stirring that with median size is 25 μ m contains in the diethylene glycol monomethyl ether solution of 5% diethylenetriamine (weight ratio, down with), 15% KH-550 and 20% dilute hydrochloric acid (original content 15%) to 300ml.With the ultrasonication 10min of 300W power, place 900W power microwave generator to stir again earlier, put into the water coolant inner coil pipe, microwave generator is by half-full power work, and the control temperature of reaction system is no more than 110 ℃, coreaction 20min.Filter and obtain polymer powder, with washing with alcohol 3 times (each 200ml ethanol), vacuum-drying.It is 100:14.3 that XPS records polymer beads surface C/Si atomic ratio.Measure with MasterSizer 2000 type laser particle size analyzers (Britain Ma Erwen company), mean particle size does not almost change, and still is about 25 μ m.
Reference examples 1(heats graft reaction):
100g polymethylmethacrylate (PMMA) the powder dispersed with stirring that with median size is 25 μ m contains in the diethylene glycol monomethyl ether solution of 5% diethylenetriamine (weight ratio, down with), 15% KH-550 and 20% dilute hydrochloric acid (original content 15%) to 300ml.With the ultrasonication 10min of 300W power, place the oil bath heating unit more earlier, stirrer, return line are installed, heated and stirred, 110 ℃ of controlled temperature, coreaction 2 hr.Filter and obtain polymer powder, with washing with alcohol 3 times (each 200ml ethanol), vacuum-drying.It is 100:3.5 that XPS records polymer beads surface C/Si atomic ratio.
Embodiment 2:
100g polymethylmethacrylate (PMMA) the powder dispersed with stirring that with median size is 5 μ m contains in the diethylene glycol monomethyl ether solution of 5% diethylenetriamine (weight ratio, down with), 20% diethylenetriamine base propyl trimethoxy silicane (A-1130 of prestige section) and 30% dilute hydrochloric acid (original content 15%) to 300ml.With the ultrasonication 10min of 300W power, place 900W power microwave generator to stir again earlier, put into the water coolant inner coil pipe, microwave generator is by 50% full power operation, and the control temperature of reaction system is no more than 110 ℃, coreaction 30min.Filter and obtain polymer powder, with washing with alcohol 3 times (each 200ml ethanol), vacuum-drying.It is 100:16.2 that XPS records polymer beads surface C/Si atomic ratio.Measure with MasterSizer 2000 type laser particle size analyzers (Britain Ma Erwen company), mean particle size does not almost change, and still is about 5 μ m.
Embodiment 3:
With median size is that 100g polymethylmethacrylate (PMMA) the powder dispersed with stirring of 780 μ m contains 5% diethylenetriamine (weight ratio to 300ml, down with), 10% N, N-is two-the diethylene glycol monoethyl ether solution of (triethoxysilylpropyl) imines (G-402) and 10% dilute hydrochloric acid (original content 15%) in.With the ultrasonication 10min of 300W power, place 900W power microwave generator to stir again earlier, put into the water coolant inner coil pipe, microwave generator is by 80% full power operation, and the control temperature of reaction system is no more than 110 ℃, coreaction 8min.Filter and obtain polymer powder, with washing with alcohol 3 times (each 200ml ethanol), vacuum-drying.It is 100:21.5 that XPS records polymer beads surface C/Si atomic ratio.Measure with MasterSizer 2000 type laser particle size analyzers (Britain Ma Erwen company), mean particle size does not almost change, and still is about 780 μ m.
Embodiment 4:
With median size is that 100g polyvinyl chloride (PVC) the powder dispersed with stirring of 180 μ m contains in the diethylene glycol monoethyl ether solution of 15% diethylenetriamine propyl trimethoxy silicane (A-1130 of prestige section) and 20% dilute hydrochloric acid (original content 15%) to 300ml, elder generation is with the ultrasonication 10min of 300W power, place 900W power microwave generator to stir again, put into the water coolant inner coil pipe, microwave generator is by half-full power work, the control temperature of reaction system is no more than 110 ℃, coreaction 15min.Filter and obtain polymer powder, with washing with alcohol 3 times (each 200ml ethanol), vacuum-drying.It is 100:25.1 that XPS records polymer beads surface C/Si atomic ratio.
Embodiment 5:
With median size is 100g vinyl acetate-ethylene copolymer (EVA of 56 μ m, VA 56%) the powder dispersed with stirring contains in the diethylene glycol monoethyl ether solution of 10% γ-azido-propyl-triethoxysilicane, 5% dicumyl peroxide and 20% dilute hydrochloric acid (original content 15%) to 300ml, ultrasonication 10min, place in the microwave generator, feed the water coolant inner coil pipe, open microwave generator, by half-full power work, stirring reaction 20min, controlled temperature are no more than 110 ℃.Filter and obtain polymer powder, with washing with alcohol 3 times (each 200ml ethanol), vacuum-drying.It is 100:9.4 that XPS records polymer beads surface C/Si atomic ratio.
Embodiment 6:
With median size is that 100g polyvinyl acetate (PVA) (PVAc) the powder dispersed with stirring of 88 μ m contains in the diethylene glycol monoethyl ether solution of 10% γ-azido-propyl-triethoxysilicane, 5% dicumyl peroxide and 20% dilute hydrochloric acid (original content 15%) to 300ml, ultrasonication 10min, place in the microwave generator, feed the water coolant inner coil pipe, open microwave generator, by half-full power work, stirring reaction 20min, controlled temperature are no more than 110 ℃.Filter and obtain polymer powder, with washing with alcohol 3 times (each 200ml ethanol), vacuum-drying.It is 100:10.6 that XPS records polymer beads surface C/Si atomic ratio.
Embodiment 7
With median size is that the 100g styrene-butadiene rubber(SBR) powder dispersed with stirring of 210 μ m contains in the Diethylene Glycol monoacetate solution of 15% gamma-mercaptopropyltriethoxysilane (KH-580), 3% benzoyl peroxide and 20% dilute hydrochloric acid (original content 15%) to 300ml, elder generation is with the ultrasonication 10min of 300W power, place 900W power microwave generator to stir again, put into the water coolant inner coil pipe, microwave generator is by 80% full power operation, the control temperature of reaction system is no more than 110 ℃, coreaction 20min.Filter and obtain polymer powder, with washing with alcohol 3 times (each 200ml ethanol), vacuum-drying.It is 100:17.9 that XPS records polymer beads surface C/Si atomic ratio.
Embodiment 8
With median size is that the 100g recycling round tire rubber powder of 1800 μ m (is called the raw material rubber powder, or being called unmodified rubber powder) dispersed with stirring contains 15% pair of (the silica-based propyl group of triethoxy) disulphide (Z-6820) to 300ml, in the Diethylene Glycol monoacetate solution of 3% benzoyl peroxide and 20% dilute hydrochloric acid (original content 15%), elder generation is with the ultrasonication 10min of 300W power, place 900W power microwave generator to stir again, put into the water coolant inner coil pipe, microwave generator is by 80% full power operation, the control temperature of reaction system is no more than 110 ℃, coreaction 15min.Filter and obtain polymer powder (being called modified glue powder), with washing with alcohol 3 times (each 200ml ethanol), vacuum-drying.It is 100:14.4 that XPS records polymer beads surface C/Si atomic ratio.
Application Example 1:
The improvement of surface modification polymer powder-coagulating cement soil composite material impelling strength.
Starting material:
No. 400 cement of Guangzhou Shi Jing; Wash the dry river sand that sieves, apparent density 2.7 g/cm
3, fineness modulus 1.51; Embodiment 8 modified glue powders and embodiment 8 raw materials used rubber powders.
The product batching:
1) preparation of normal concrete test specimen
With cement, river sand and water by water cement ratio be respectively 0.35 and 0.40(according to weight), intensity rank is that the concrete examination method of completing the square of C30 is tried to join, corresponding proportioning is designed to C (cement): S (river sand): W (water)=1:3.91:0.35(is according to weight), corresponding cement consumption is respectively 457.1Kg/m
3Each component that will prepare material is then made the normal concrete test test specimen of respective performances through stirring, moulding, and natural curing 28 days is stand-by.
2) unmodified rubber powder matrix material test material preparation
With the rubber powder of non-modified, press the quality percentage composition of cement consumption in the benchmark test specimen, from 0% to 50%, be incorporated into respectively in the batching of benchmark test specimen, stir, moulding, respective performances test test specimen is made in natural curing 28 days, and is stand-by.
3) apply the test material preparation of modified glue powder matrix material
The rubber powder of non-modified is sprayed silane resin acceptor kh-550, after the oven dry, according to the above ratio with the method product, natural curing 28 days.
4) modified glue powder matrix material test material preparation
Rubber powder after embodiment 8 graft modifications is pressed the quality percentage composition of cement consumption in the benchmark test specimen, from 0% to 50%, be incorporated into respectively in the batching of benchmark test specimen, stir, moulding, respective performances test test specimen is made in natural curing 28 days, and is stand-by.
The impelling strength test adopts the method for regulation in the material of construction standard compilation to carry out on MZ – 2069 type drop hammer impact testing machines (Jiangdu Mingzhu Testing Machinery Co., Ltd.).
1) sample dimensions
Sample dimensions is the cube specimen of 100mm * 100mm * 100mm.
Test procedure
1. with the level correction of equipment work platform, test specimen is placed on the worktable then.
2. use steel ball in the certain altitude free-falling, pound, destroy until test specimen on the test specimen surface.
3. write down steel ball whereabouts number of times.
(3) result calculates
The impelling strength of concrete composite material can be calculated as follows:
Wherein:
a k : test specimen impelling strength (J/cm
2)
M: steel ball weight (kg)
N: steel ball whereabouts number of times
S: test specimen cross-sectional area (cm
2)
H: steel ball height of drop (cm)
G: universal gravity constant
Record the impelling strength of each composite product, the mapping contrast, as shown in Figure 1.
Claims (10)
1. the polymer solid particles of a surface modification, wherein surface modification is to realize by introduced the alkoxysilane groups that can react on the polymer beads surface, and the C/Si atomic ratio that is recorded the polymer beads surface by x-ray photoelectron spectroscopy (XPS) is 100: 6-30, preferred 100: 9-26; Wherein got rid of or do not comprised polysiloxane or polysiloxane copolymer by the polymkeric substance of surface modification.
2. the polymer solid particles of 1 of claim surface modification, wherein the median size of this solid particulate is the 5-800 micron.
3. the polymer solid particles of 1 of claim or 2 surface modification, wherein this polymkeric substance be selected from (methyl) Voncoat R 3310 or its multipolymer, ryuron or its multipolymer, leifa, polyethylene-vinyl acetate copolymer, the styrene-butadiene rubber(SBR) one or both or multiple, or this polymkeric substance is the matrix material that is formed by these polymer materialss and carbon black or other mineral filler.
4. the polymer solid particles of the surface modification of any one among the claim 1-3, wherein the alkoxysilane groups that can react is via being chemically bonded on the polymer solid particles surface.
5. the polymer solid particles of the surface modification of any one among the claim 1-4, wherein the alkoxysilane groups that can react is selected from Trimethoxy silane base (CH
3O)
3Si-R-, triethoxysilicane alkyl (CH
3CH
2O)
3Si-R-, and their incomplete hydrolytic condensation form, wherein-the R-group includes but not limited to-CH
2-,-CH
2CH
2-or-CH
2CH
2CH
2-.
6. the preparation method who prepares the surface modification polymer solid particles of any one among the claim 1-5, this method comprise with as the polymer solid particles suspended dispersed of starting raw material in a kind of organic solvent-diluted mineral acid mixed system that is dissolved with the silane coupling agent that contains functional group and optional multifunctional linking agent, carry out surface modification by means of microwave action by solid particulate then so that will contain on the surface that the silane coupling agent of functional group is bonded to polymer beads, this functional group is selected from amino (being primary amino and/or secondary amino group), sulfydryl, bisthioether linkage, a kind of functional group in polythiaether key or the azido-; Wherein, alkoxysilane groups is chemically bonded on the polymer solid particles surface by these functional groups on the silane coupling agent and the chemical reaction between the polymer chain in the polymer solid particles, thus the polymer solid particles of acquisition surface modification.
7. claim 6 method, wherein the polymer beads as raw material does not dissolve in employed organic solvent-diluted mineral acid mixed system, and employed organic solvent be in alcohols, ester class, ketone, the ether solvent one or both or multiple.
8. claim 6 or 7 method, wherein as the polymkeric substance in the polymer solid particles of raw material be selected from (methyl) Voncoat R 3310 or its multipolymer, ryuron or its multipolymer, leifa, polyethylene-vinyl acetate copolymer, the styrene-butadiene rubber(SBR) one or both or multiple, or the matrix material that forms of these polymkeric substance and carbon black or other mineral filler.
9. the method for claim 6, wherein surface modification is following carrying out: the reaction vessel that polymer solid particles is housed that will be connected with reflux condensing tube places microwave reactor, microwave operational frequencies is 2400-2500Hz, every kilogram material polymer solid particles configuration microwave power is 400-9000 watt, be preferably 4500-9000 watt, reaction times 8-30 minute.
10. the polymer solid particles of the surface modification of claim 1 is used for the purposes that the cement concrete material system is improved its impelling strength.
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| CN105735935A (en) * | 2016-03-07 | 2016-07-06 | 平顶山市安泰华矿用安全设备制造有限公司 | Gas drainage borehole sealing process |
| CN105860139A (en) * | 2016-05-13 | 2016-08-17 | 嘉兴北化高分子助剂有限公司 | Modifying coupling agent master batch and preparation method thereof |
| CN107366409A (en) * | 2017-08-07 | 2017-11-21 | 安徽温禾新材料科技股份有限公司 | A kind of production technology of Environmental protection floor base material maize straw base flame retardant type composite plate |
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| CN111170321A (en) * | 2020-01-06 | 2020-05-19 | 同济大学 | Preparation method of nano hollow sphere containing graphitized carbon dots |
| CN111334146A (en) * | 2020-04-22 | 2020-06-26 | 南京东顶新材料科技有限公司 | Long-acting anticorrosion water-based cold-coating zinc coating and preparation method thereof |
| CN112110430A (en) * | 2020-09-23 | 2020-12-22 | 中国矿业大学 | Method for improving solubility of black phosphorus of two-dimensional material |
| CN113980280A (en) * | 2021-11-17 | 2022-01-28 | 安徽沸点新材料有限公司 | Organosilane coupling agent and preparation method thereof |
| CN113980577A (en) * | 2021-10-26 | 2022-01-28 | 厦门锶特材料科技有限公司 | Prehydrolysis organic silicon precursor composition for stone protection and preparation method thereof |
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| CN101735633A (en) * | 2009-11-26 | 2010-06-16 | 同济大学 | Functionalized organic/inorganic hybridized asymmetric structure particle and synthesis method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101735633A (en) * | 2009-11-26 | 2010-06-16 | 同济大学 | Functionalized organic/inorganic hybridized asymmetric structure particle and synthesis method thereof |
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| CN107366409A (en) * | 2017-08-07 | 2017-11-21 | 安徽温禾新材料科技股份有限公司 | A kind of production technology of Environmental protection floor base material maize straw base flame retardant type composite plate |
| CN107540904A (en) * | 2017-08-07 | 2018-01-05 | 安徽温禾新材料科技股份有限公司 | A kind of modified rubber powder Wood composite material for mute floor board and preparation method thereof |
| CN111170321A (en) * | 2020-01-06 | 2020-05-19 | 同济大学 | Preparation method of nano hollow sphere containing graphitized carbon dots |
| CN111170321B (en) * | 2020-01-06 | 2023-03-24 | 同济大学 | Preparation method of nano hollow sphere containing graphitized carbon dots |
| CN111334146A (en) * | 2020-04-22 | 2020-06-26 | 南京东顶新材料科技有限公司 | Long-acting anticorrosion water-based cold-coating zinc coating and preparation method thereof |
| CN111334146B (en) * | 2020-04-22 | 2022-01-04 | 南京东顶新材料科技有限公司 | Long-acting anticorrosion water-based cold-coating zinc coating and preparation method thereof |
| CN112110430A (en) * | 2020-09-23 | 2020-12-22 | 中国矿业大学 | Method for improving solubility of black phosphorus of two-dimensional material |
| CN112110430B (en) * | 2020-09-23 | 2021-11-09 | 中国矿业大学 | Method for improving solubility of black phosphorus of two-dimensional material |
| CN113980577A (en) * | 2021-10-26 | 2022-01-28 | 厦门锶特材料科技有限公司 | Prehydrolysis organic silicon precursor composition for stone protection and preparation method thereof |
| CN113980280A (en) * | 2021-11-17 | 2022-01-28 | 安徽沸点新材料有限公司 | Organosilane coupling agent and preparation method thereof |
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