CN102786829B - Preparation method and using method of water curing putty product - Google Patents
Preparation method and using method of water curing putty product Download PDFInfo
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- CN102786829B CN102786829B CN201210268686.3A CN201210268686A CN102786829B CN 102786829 B CN102786829 B CN 102786829B CN 201210268686 A CN201210268686 A CN 201210268686A CN 102786829 B CN102786829 B CN 102786829B
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Abstract
The invention discloses a preparation method of a water curing putty product. The preparation method comprises the following steps: 30-35 parts by weight of unsaturated base resin modified by dicyclopentadiene is taken as a main base material, the main base material, 14.5-25 parts by weight of auxiliary base material prepared from calcined products of water-cooling dregs from a steel mill and an iron mill and calcium sulfate hemihydrates are put into a high-speed dispersion machine and dispersed uniformly, then a certain amount of auxiliary initiator, air hole sealant, stabilizing agent, dispersing agent, filling agent and the like are sequentially added, and after a uniform paste body is formed, the uniform paste body is put into a colloid mill to be milled to obtain a product with the needed fineness. The water curing putty product has the advantage of completely meeting related standards, and has outstanding environmental protection performance, safety and economy.
Description
Technical field
The present invention relates to a kind of preparation method of water cure putty product.
Background technology
The product surface of the manufacturings such as rolling stock, automobile, motor all needs decoration, pointing putty is all wanted during decoration application, current domestic conventional putty has atomized ash, epoxide modified putty, body solder, the body solder of PPG company, the Unsaturated polyester putty etc. of Japanese ippon company of Ze You du pont company abroad, their common features be under normal temperature solid fast, strong adhesion, workability are better.But the solidifying agent that they are used and initiator are all organo-peroxides.It is unfavorable to operator ' s health that this traditional solidifying agent can discharge offending smell, and belong to combustible and explosive articles, perishable and have potential safety hazard in production, transport, really haves much room for improvement.
Summary of the invention
The object of this invention is to provide a kind of preparation method of water cure putty product, it makes solidifying agent with water, workability at normal temperatures, dry and solid characterisc, sticking power, snappiness, shock resistance and all can reach the requirement of Ministry of Railways ministerial standard TB/T2393-2001 with technical indicators such as end overcoatabilities, and possess the outstanding feature of environmental protection, security and economy.
Technical scheme of the present invention is, a kind of preparation method of water cure putty product, it is characterized in that: the preparation method of this putty product comprises following steps---get the dicyclic pentylene modified unsaturated group vibrin of 30-35 weight parts and to decide base-material, the structural formula of described unsaturated group vibrin is
r is wherein dibasic alcohol, will take from steel mill, water-cooled slag in ferroalloy works' iron manufacturing process is calcined in retort furnace at 1300-1400 DEG C, add 3-5wt.% calcium sulphate hemihydrate after cooling is ground to 300-400 orders again and become 14.5 altogether---the auxiliary base-material of 25 weight parts, by described main base-material, auxiliary base-material adds co initiator 4-5.3 weight part after dropping into and being fully uniformly dispersed in the high speed dispersor of 1500-1800L/min in order gradually, pore encapsulant 4---5.5 weight parts, adhesive promoter 3-4 weight part, stablizer 1-1.88 weight part, thixotropic agent 3-4 weight part, dispersion agent 0.17-0.19 weight part, weighting agent 20-32.9 weight part and toning agent 4-5 weight part, be ground to fineness≤50um to reentering colloid mill after forming even body of paste namely to obtain the putty packing of product stand-by, described co initiator is peroxidation sulfuric acid potassium, sodium, ammonium salt, described pore encapsulant is the active film forming glue with cis-butenedioic anhydride graft modification based on polystyrene, described adhesive promoter is the PVP Virahol/vinyl toluene mixing solutions of 3-5vot.%, described stablizer is that cis-butenedioic anhydride adds copper naphthenate or adds copper naphthenate along acid, described thixotropic agent is silicon-dioxide wilkinite, and described dispersion agent is sodium laurylsulfonate, sodium lauryl sulphate, described weighting agent is talcum powder, dicalcium powder, and described toning agent is titanium dioxide, zinc sulfide white or ultramarine, the using method of this putty product gets 100 weight part paste putty products, adds the tap water of 10-15 weight part pH value 7-8, well water or river wherein, stir.
The invention has the beneficial effects as follows: not only all technical all meets the regulation of Ministry of Railways ministerial standard TB/T2393-2001, and there is the outstanding feature of environmental protection, security and economy.
Embodiment
A method of preparation and use for water cure putty product, is characterized in that: the preparation method of this putty product comprises following steps---get the dicyclic pentylene modified unsaturated group vibrin of 30-35 weight parts and to decide base-material, the structural formula of this resin is
wherein R represents dibasic alcohol, will take from steel mill, water-cooled slag in ferroalloy works' iron manufacturing process is calcined in retort furnace at 1300-1400 DEG C, add 3-5wt.% calcium sulphate hemihydrate after cooling is ground to 300-400 orders again and become 14.5 altogether---the auxiliary base-material of 25 weight parts, by described main base-material, auxiliary base-material adds co initiator 4-5.3 weight part after dropping into and being fully uniformly dispersed in the high speed dispersor of 1500-1800L/min in order gradually, pore encapsulant 4---5.5 weight parts, adhesive promoter 3-4 weight part, stablizer 1-1.88 weight part, thixotropic agent 3-4 weight part, dispersion agent 0.17-0.19 weight part, weighting agent 20-32.9 weight part and toning agent 4-5 weight part, be ground to fineness≤50um to reentering colloid mill after forming even body of paste namely to obtain the putty packing of product stand-by, described co initiator is peroxidation sulfuric acid potassium, sodium, ammonium salt, described pore encapsulant is the active film forming glue with cis-butenedioic anhydride graft modification based on polystyrene, described adhesive promoter is the PVP Virahol/vinyl toluene mixing solutions of 3-5vot.%, described stablizer is cis-butenedioic anhydride or suitable sour and copper naphthenate, described thixotropic agent is silicon-dioxide wilkinite, and described dispersion agent is sodium laurylsulfonate, sodium lauryl sulphate, described weighting agent is talcum powder, dicalcium powder, and described toning agent is titanium dioxide, zinc sulfide white or ultramarine, the using method of this putty product gets 100 weight part paste putty products, adds the tap water of 10-15 weight part pH value 7-8, well water or river wherein, stir.
It is below the allocation sheet of specific embodiment.
Four its technology quality index of Example formulations in table all meet the regulation of TB/T2393-2001.
Shown in four embodiments, raw materials quality character is constant, just have adjusted the quantity that each formula is taken, and its preparation technology's flow process is the same.The repeatable water cure putty product of the present invention preparing effect stability in these four kinds of Example formulations.
Putty product of the present invention can be with the reason of water generation curing reaction under normal temperature:
1. the main base-material of putty have employed a kind of dicyclic pentylene modified unsaturated group vibrin, and this resin air-drying property is good, and cost is relatively lower, and it is the same easy generation cross-linking polymerization with all unsaturated group resins.At Curing agent (i.e. co initiator in the present invention) and promotor (the calcium hydroxide Ca (OH) namely generated in the present invention's formula
2) effect under produce free radical cause double bond, cause cross-linking polymerization
When adding water in putty, water and auxiliary base-material generation hydration reaction generating portion Ca (OH)
2, this facilitates again the decomposition of co initiator in putty and produces radical.Vinyl monomer in main base-material (unsaturated group vibrin) in radical initiation putty and polyester play polyaddition reaction.
2. the auxiliary base-material in putty composition comprises 3CaAl
2o
3(tricalcium aluminate), 3CaOSiO
2)(tricalcium silicate); 2CaOSiO
2(Dicalcium Phosphate (Feed Grade)) 4CaOAl
2o
3fe
2o
3(tetracalcium aluminoferrite) and calcium sulphate hemihydrate, these are all the materials that Yi Yushui carries out hydration reaction.Reaction mechanism is schematically as follows:
A, tricalcium silicate (3CaOSiO
2), Dicalcium Phosphate (Feed Grade) (2CaOSiO
2) and water generation hydration reaction, generate gel state crystalline hydrate---hydrated calcium silicate;
2(3CaO·SiO
2)+6H
2O＝3CaO·2SiO
2·H
2O+3Ca(OH)
2
2(2CaO·SiO
2)+6H
2O＝3CaO·2SiO
2·H
2O+Ca(OH)
2
B, tricalcium aluminate (3CaAl
2o
3), tetracalcium aluminoferrite (4CaOAl
2o
3fe
2o
3) generate gel crystalline hydrate with water generation hydration reaction:
3CaO·Al
2O
3+6H
2O＝3CaO·Al
2O
3·6H
2O
4CaO?Al
2O
3?Fe
2O
3+4Ca(OH)
2+22H
2O＝4CaO·Al
2O
3·13H
2O+4CaO·Fe
2O
3·13H
2O
C, part Ca (OH) owing to also having calcium sulfate and hydration reaction to generate in the auxiliary base-material of putty
2can continue following reaction occurs with hydration reaction thing, form calcium ferrite class, calcium aluminate class hydration solids
3CaO·Al
2O
3·6H
2O+3CaSO
4+25H
2O＝3CaO·Al
2O
3·3CaSO
4·31H
2O
CaO·Fe
2O
3(2-6)H
2O+2Ca(OH)
2+X?H
2O＝3CaO·Fe
2O
3·X?H
2O
3CaO·Al
2O
3·6H
2O+Ca(OH)
2+12H
2O＝4CaO·Al
2O
3·19H
2O
3. the reaction of major-minor solidifying agent (also known as major-minor initiator, water and inorganic peroxygen salt) and putty base-material:
Co initiator (inorganic peroxygen salt) is as only water-soluble in peroxidation sulfuric acid potassium, sodium, ammonium salt, be insoluble in organic solvent and resin, usually co initiator added in the main base-material (resin) of putty in putty preparation process.
When constructing, main initiator water is joined in putty, co initiator in putty meets very fast dissolving of water meeting and cross-linking polymerization occurs the main base-material (resin) produced in radical initiation putty, and water and the auxiliary base-material generation hydration reaction (gel) in putty, produce again Ca (OH) in hydration reaction process simultaneously
2the co initiator in putty is facilitated so again to decompose generation radical further, these radicals accelerate again to cause main base-material in putty and contained vinyl monomer and unsaturated polyester and play polyaddition reaction, finally make main initiator (water) co initiator (inorganic peroxygen salt) in putty all run out, putty also by time rare paste body be solidified into solids gradually.
By above steps achieve use water as the putty product that solidifying agent makes the present invention prepare can under room temperature (normal temperature) dry (solidification).
4. the auxiliary base-material (3CaOAl of water cure putty of the present invention
2o
3, 3CaOSiO
2, 2CaOSiO
2, CaSO
4, 4CaOAi
2o
3fe
2o
3) etc. mixture adopt 0.3-0.5% PEG or stearic Virahol/ethyl acetate solution carry out coated pre-treatment, achieve the auxiliary base-material hydration reaction delayed in putty speed and be easy to disperse effect.
5. with the addition of di-carboxylic acid (cis-butenedioic anhydride adds copper naphthenate or adds copper naphthenate along acid) one package stabilizer in water cure putty of the present invention, di-carboxylic acid can in and putty assist the free lime alkali Ca (OH) brought in base-material
2, reduce its promotor effect in putty stores thus extend storage period of putty, the adding of copper naphthenate can delay putty and use the crosslinking polymerization speed at initial stage but can promote that putty is coated with the polyaddition reaction speed of scraping the film forming later stage.Thus ensure that putty product adaptation is coated with the time requirement of scraping construction in big area.
6. the pore encapsulant, in water cure putty product of the present invention composition be based on polystyrene with the strong cis-butenedioic anhydride of polarity to the active film forming glue of the one after its graft modification, its reaction mechanism schematically as follows:
Adding of this encapsulant, a part can participate in crosslinking reaction with the main base-material of putty; A part is free on putty membrane surface, can the pore of confining surface effectively in the putty membrane solid later stage, in order to waterproof and follow-up paint application.
Claims (4)
1. the preparation method of a water cure putty product, it is characterized in that: the preparation method of this putty product comprises following steps---get the dicyclic pentylene modified unsaturated group vibrin of 30-35 weight parts and to decide base-material, the structural formula of described unsaturated group vibrin is
r is wherein dibasic alcohol, will take from steel mill, water-cooled slag in ferroalloy works' iron manufacturing process is calcined in retort furnace at 1300-1400 DEG C, add 3-5wt.% calcium sulphate hemihydrate after cooling is ground to 300-400 orders again and become 14.5 altogether---the auxiliary base-material of 25 weight parts, by described main base-material, auxiliary base-material adds co initiator 4-5.3 weight part after dropping into and being fully uniformly dispersed in the high speed dispersor of 1500-1800L/min in order gradually, pore encapsulant 4---5.5 weight parts, adhesive promoter 3-4 weight part, stablizer 1-1.88 weight part, thixotropic agent 3-4 weight part, dispersion agent 0.17-0.19 weight part, weighting agent 20-32.9 weight part and toning agent 4-5 weight part, be ground to fineness≤50um to reentering colloid mill after forming even body of paste namely to obtain the putty packing of product stand-by, described co initiator is peroxidation sulfuric acid potassium, sodium, ammonium salt, described pore encapsulant is the active film forming glue with cis-butenedioic anhydride graft modification based on polystyrene, described adhesive promoter is the PVP Virahol/vinyl toluene mixing solutions of 3-5vot.%, described stablizer is that cis-butenedioic anhydride adds copper naphthenate or adds copper naphthenate along acid, described thixotropic agent is silicon-dioxide wilkinite, and described dispersion agent is sodium laurylsulfonate, sodium lauryl sulphate, described weighting agent is talcum powder, dicalcium powder, and described toning agent is titanium dioxide, zinc sulfide white or ultramarine.
2. the preparation method of water cure putty as claimed in claim 1, it is characterized in that, auxiliary base-material in its raw material composition is a kind of easy generation hydration reaction, by tricalcium aluminate, tricalcium silicate, Dicalcium Phosphate (Feed Grade), the inorganic powder mixture of tetracalcium aluminoferrite and calcium sulphate hemihydrate composition, wherein containing tricalcium aluminate 6-15%, containing tricalcium silicate 45-60%, containing Dicalcium Phosphate (Feed Grade) 10-30%, containing tetracalcium aluminoferrite 5-10%, steel mill taken from by auxiliary base-material, a kind of water-cooled slag in ferroalloy works' iron manufacturing process, it can meet the requirement of above-mentioned mass component, tricalcium silicate wherein, Dicalcium Phosphate (Feed Grade) can generate gelatinous hydrated calcium silicate with water generation hydration reaction, and tricalcium aluminate, tetracalcium aluminoferrite also reacts with water and generates gel crystalline hydrate aquation tricalcium aluminate and aquation tetracalcium aluminoferrite.
3. the preparation method of a kind of water cure putty as claimed in claim 1, it is characterized in that the inorganic peroxide co initiator adopted in raw material is only water-soluble, be insoluble in organic solvent and resin, usually it is added in the main binder resin of putty in putty preparation process, the highly stable storage being beneficial to the putty product long period when not running into water, after adding become owner of initiator water when constructing, main binder resin in putty and contained vinyl unit generation cross-linking polymerization can be caused and make putty solid by very fast generation radical soluble in water.
4. the preparation method of water cure putty as claimed in claim 1, the object that it is characterized in that adding blowhole encapsulant is the pore that the solid process of closed putty is formed, strengthen the water-fast erosion resistance of Bulk coat, described pore encapsulant is the active film forming glue of one of cis-butenedioic anhydride graft modification strong by polarity based on polystyrene, and the reaction process of preparation is as follows:
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|---|---|---|---|
| CN201210268686.3A CN102786829B (en) | 2012-07-31 | 2012-07-31 | Preparation method and using method of water curing putty product |
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| CN102786829B true CN102786829B (en) | 2015-01-14 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696331A (en) * | 2009-10-30 | 2010-04-21 | 株洲市华晟实业有限公司 | Flame-retarding lacquer putty and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6142574A (en) * | 1984-08-03 | 1986-03-01 | Nippon Synthetic Chem Ind Co Ltd:The | Unsaturated polyester resin composition for coating |
| JP2002322423A (en) * | 2001-04-24 | 2002-11-08 | Dainippon Ink & Chem Inc | Resin composition for putty and putty |
| CN102443114B (en) * | 2010-10-13 | 2013-11-06 | 常州华科树脂有限公司 | Air-dried unsaturated polyester resin with excellent comprehensive property and its preparation method |
| CN102250504B (en) * | 2011-06-20 | 2013-01-23 | 石家庄市油漆厂 | High temperature resistant automobile special putty not influencing adhesion and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696331A (en) * | 2009-10-30 | 2010-04-21 | 株洲市华晟实业有限公司 | Flame-retarding lacquer putty and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 环保型水固化不饱和基腻子的制备;刘之礼等;《涂料工业》;20120930;第42卷(第9期);第32-35页 * |
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