CN107011791B - A kind of organic-inorganic composite shop primer of not zincilate and preparation method thereof - Google Patents
A kind of organic-inorganic composite shop primer of not zincilate and preparation method thereof Download PDFInfo
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- CN107011791B CN107011791B CN201710013457.XA CN201710013457A CN107011791B CN 107011791 B CN107011791 B CN 107011791B CN 201710013457 A CN201710013457 A CN 201710013457A CN 107011791 B CN107011791 B CN 107011791B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/02—Polysilicates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/02—Polysilicates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of organic-inorganic composite shop primers and preparation method thereof of not zincilate, the organic-inorganic composite shop primer of zincilate is not made of component A and B component, component A is by 10 seconds 3.0~5.0 parts by weight of polyvinyl butyral, 0.3~0.6 parts by weight of polyamide wax pulp, 15~17.0 parts by weight of dehydrated alcohol, 5~9 parts by weight of butanol, 7~10 parts by weight of phosphorus titanium valve, 35~45 parts by weight of ferrophosphorus powder composition, component A total amount are 80 parts by weight；B component is by 20 parts by weight of ethyl polysilicate of 40~42% dioxide-containing silicas of polyurethane-modified dose of 50% modified degree of hydrolysis；This is free of zinc shop primer, there is better film forming than traditional ethyl orthosilicate partial hydrolystate, Corrosion Protection overcomes the disadvantage without zinc shop primer film forming difference and Corrosion Protection difference close to the solvent type inorganic primer for zinc silicate shop of the pure zinc powder of tradition.
Description
Technical field
The present invention relates to a kind of shop primers, and in particular to a kind of compound no zinc-type shop primer.
Background technique
Shop primer be also known as steeis pretreament priming paint or maintenance priming paint (Prefabr cation Primer), be steel plate or
One layer of antirust paint that fashioned iron sprays on assembly line after ball blast pretreatment derusting.The effect of shop primer is to by ball blast
The steel surface of reason is protected, and prevents that steel from getting rusty during processing and shipbuilding and bring is corrosion-damaged.In ship
With large-scale iron structure etc. build in it is very widely used.
Shop primer mainly has polyvinyl butyral shop primer (PVB), Epoxy Zinc-Rich Shop Primer, epoxy iron red shop vehicle
Between four seed type of priming paint and inorganic primer for zinc silicate shop.There are also the shop primers of some other types, such as acrylic acid iron oxide red vehicle
Between priming paint etc., using and few, wherein inorganic primer for zinc silicate shop, with good heat resistance, rust-preventing characteristic outstanding, with
And with the good compatibility performance of other coatings.Inorganic primer for zinc silicate shop using ethyl orthosilicate as base-material, be equipped with zinc powder and
Other pigment, filler, solvent, additive etc. are made.It has extremely strong rust-preventing characteristic, the inorganic zinc silicate workshop bottom of high zinc content
Antirust is painted up to 9~14 months.Damage surface is few when inorganic primer for zinc silicate shop good mechanical performance, heat-resist, hot-working
Equal outstanding properties.
Shop primer will meet following technical indicator:
1 shop primer technical indicator of table
Note: 1. 4 grades in weatherability index refer to that the area for rust spot occur is no more than 50%.
2. being guarantee project.
3. being guarantee project.
Shop primer is different from common coating, has the characteristics that following:
(1) shop primer is a kind of priming paint of interim maintenance, has certain performance for preventing steel plate corrosion, defects liability period
Limit generally 3~9 months.The shop primer at Long Term Contact seawater position has the non-saponifying performance of cathodic protection.
(2) can be good at the needs for meeting automatic assembly line operation, paint film surface drying in 3~5min.Generally drying
Under the conditions of dry, surface of steel plate temperature is 40 DEG C, and shop primer is dry in 3min, guarantee moved on raceway and in lifting not
Damage paint film.
(3) the film thickness of shop primer is relatively thin, using airless spraying and can obtain uniform film.Containing zinc or be free of zinc
The thickness of shop primer is respectively 15~20um and 15~25um；The film thickness of shop primer is generally not counted in the total of the coating of hull
In film thickness.
(4) shop primer does not have an impact the welding performance of steel plate, does not influence weld strength.
(5) shop primer does not contain the pigment of arsenic, antimony, lead, chromium, cadmium.In cutting or welding, paint film generate smog and
Dust etc. is harmless, and the poisonous and harmful substance concentration of release is within the scope of national health index is permitted.
(6) paint film satisfactory mechanical property is resistant to frictional impact when carrying, bending when including processing, and by coating
Various coating have good ply adhesion.
The way of inorganic primer for zinc silicate shop at present: bi-component package, component A are polyvinyl alcohol contracting butyric acid, without watery wine
Essence, zinc powder；B component is alcohol solvent type partial hydrolysis ethyl orthosilicate, the i.e. ethyl orthosilicate of partial hydrolysis.
Current this kind of coating there are the problem of and defect:
Zinc-rich type since zinc powder is active amphoteric metal, it is easy to sent out with the ethyl orthosilicate of the partial hydrolysis of hydroxyl
Raw cross-linking reaction forms the film of rigid after dry, but the resource of zinc powder is limited, and zinc powder price is high, and uses phosphorus titanium valve
With phosphorus ferrous powder metal rust resisting pigment, it is desirable to which also like using zinc powder such, film is hard, but uses ferrophosphorus powder or phosphorus titanium valve, then
It is that film is very soft, quite like " soybean residue ", film forming is poor, becomes the hard nut to crack of long-standing problem paint industry.
Primary reason be it is low as the molecular weight of the basic material of partial hydrolystate due to generalling use ethyl orthosilicate,
Bad adhesion, property are crisp；The solid content of ethyl orthosilicate partial hydrolystate is low, and only 15~16%, not when zincilate, caking property
It is very poor.
Secondary cause is not sent out since the metallic iron of phosphorus titanium valve, ferrophosphorus powder does not have reactivity or reactivity very low
Raw cross-linking reaction, can not form fine and close film；Secondly because ferrophosphorus powder, phosphorus titanium valve density are less than zinc powder, partial hydrolysis is just
The solid content of silester is low, and pigment volume concentration (PVC) is lower, can not form hard film；Furthermore ferrophosphorus powder or phosphorus titanium valve with
Hydrogen bonding effect between base-material is bad, and film caused by wetability difference is soft.Using the ferrophosphorus powder and phosphorus titanium valve system for being free of zinc
Standby the main reason for not meeting the shop primer of technical requirements, is that traditional ethyl orthosilicate partial hydrolystate is not able to satisfy
It is required that need to develop it is a kind of can not only prepare the shop primer containing zinc, but also the silicic acid second of the shop primer without zinc can be prepared
Ester moiety hydrolysate.
In view of the above problems, develop it is a kind of all use ferrophosphorus powder or with phosphorus titanium valve mixture for rust resisting pigment
, film it is very hard, the ethyl polysilicate partial hydrolystate film forming matter of organically-modified alcohol-soluble is satisfied with to produce and is contained
Zinc or inorganic shop primer without zinc.
Summary of the invention
For the low problem of partial hydrolystate solid content existing for the country, component design improves partial hydrolysis silicic acid second
The solid content of ester；Traditionally use base-material of the ethyl orthosilicate partial hydrolystate as inorganic silicic acid spelter coating, positive silicic acid second
The molecular weight of ester is 208.3275, uses raw material of the ethyl polysilicate as partial hydrolystate instead, and 40% dioxide-containing silica gathers
The molecular weight of silester is generally 880~1000, improves its adhesiveness and flexibility；It uses better with waterproof anti-permeability
The polyurethane adducts modified polysilicate ethyl ester fraction hydrolysate of polyalcohol, improve the adhesive force of film forming matter, moisture penetration and
Fastness.
The preparation of polyurethane-modified inorganic shop primer carries out in four steps:
Polyurethane-modified dose is prepared first:
(1) polyurethane-modified dose of preparation reaction principle
TDI and propylene glycol addition, are prepared into addition product:
(2) polyurethane-modified dose of composition
According to 2.05 moles of TDI, the ratio that 1 mole of propylene glycol.That is 10~15 parts by weight of propylene glycol, toluene diisocynate
25~30 parts by weight of ester (TDI), the polyurethane of 34~36% non-volatile parts composed by 50~70 parts by weight of acetic anhydride butyl ester
Modifying agent.
(3) polyurethane-modified dose of of preparation method and step:
It is prepared in accordance with the following methods with step: the acetic anhydride butyl ester of formula ratio 1/4 being added to the container, formula is added
The propylene glycol of amount is placed in high-order dropping bath；By in acetic anhydride butyl ester and TDI the investment reaction kettle of surplus, stirring heats up
To 40~45 DEG C, starts that propylene glycol-butyl acetate solution is added dropwise, dropped evenly in 1.5~2h, uniformly heat up, drip
Temperature rise to 68~72 DEG C, and at this temperature keep 50~70 minutes, then be warming up to 74~76 DEG C keep the temperature 50~70 minutes,
When sampling and measuring nco value reaches theoretical value 7.2~7.3%, 50 DEG C are cooled to hereinafter, filling and sealing is spare.
The preparation of ethyl polysilicate partial hydrolystate
(1) ethyl polysilicate partial hydrolystate prepares reaction principle
Ethyl polysilicate and water generate ethyl polysilicate partial hydrolystate and ethyl alcohol under the action of acid catalyst:
(2) ethyl polysilicate partial hydrolystate forms
35~40 parts by weight of ethyl polysilicate that ethyl polysilicate partial hydrolystate is 40~42% by dioxide-containing silica,
3~7 parts by weight of acidifying water, 50~70 parts by weight of dehydrated alcohol are formed.
With 36% technical hydrochloric acid: glacial acetic acid=4:1 weight ratio mixed solution, the deionized water that adjustment pH value is 2~3,
As acidifying water.
(3) ethyl polysilicate partial hydrolystate preparation method and step
Ethyl polysilicate partial hydrolystate is usually prepared, degree of hydrolysis is generally 25%, and when more than 40%, storage stability is not
Good, this programme uses 40~60% degree of hydrolysis.
It carries out preparing ethyl polysilicate partial hydrolystate with method according to the following steps:
The acidifying water of formula ratio is placed in high-order dropwise adding tank, industrial ethyl polysilicate, the dehydrated alcohol of formula ratio, is added
Enter into reaction kettle, start stirring, be warming up to (60 ± 2) DEG C, starts to drop evenly acidifying water, drip within 1 hour, then heat up
To (70 ± 2) DEG C, after keeping the temperature 1.5~2h, terminal is measured with Ma beautiful jade reagent, gelling time is controlled in 150~350s, is prepared into water
Xie Du is 48~52%, the ethyl polysilicate partial hydrolystate that non-volatile part is 34~36%.
Reaction end measurement:
The hydrolysis ethyl polysilicate of 4.5ml is added in graduated 10ml scale test tube, 0.5ml morpholine is then added,
By the positive and negative shake of test tube, its gelling time is measured, general control is qualified between 150~350s at 25 DEG C.
Polyurethane-modified dose of modified polysilicate ethyl ester fraction hydrolysate
(1) modified-reaction principle
(2) composition of polyurethane-modified ethyl polysilicate partial hydrolystate
It is modified according to the matching of hydroxylated material-OH/ isocyanate addition product-NCO=2:1, consisting of polysilicon acid
100 parts by weight of ethyl ester fraction hydrolysate, polyurethane-modified dose of 130~160 parts by weight.
(3) polyurethane-modified ethyl polysilicate partial hydrolystate preparation method and step
It is prepared in accordance with the following methods with step:
First ethyl polysilicate partial hydrolystate is squeezed into dropping funel；Polyurethane-modified dose is put into there-necked flask,
50 DEG C or so are heated to, starts that ethyl polysilicate partial hydrolystate solution is added dropwise, drips within 1~1.2 hour, keep dropping temperature
No more than 70 DEG C, more than when cool down, drip after 70~75 DEG C keep the temperature 1~1.5 hour, be measured by sampling nco value be equal to theoretical value
When being 0.5~0,50 DEG C are cooled to hereinafter, filling and sealing is spare.
Detailed description of the invention
Fig. 1 is the preparation technology flow chart of polyurethane-modified ethyl polysilicate partial hydrolystate.
Specific embodiment
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of compound no zinc-type shop primers.
To achieve the above object, technical solution of the present invention is summarized as follows:
A kind of compound no zinc-type shop primer comprising there are component A and B component, by parts by weight in terms of, component A: B component
=4: 1；Wherein,
Component A includes: polyvinyl butyral 3-5 parts by weight, polyamide wax pulp 0.3-0.6 parts by weight, dehydrated alcohol 15-
17 parts by weight, butanol 5-9 parts by weight, phosphorus titanium valve 7-10 parts by weight and ferrophosphorus powder 35-45 parts by weight；
It is 48-52% that B component, which is by polyurethane-modified dose of modified degree of hydrolysis, dioxide-containing silica is the poly- of 40-42%
Silester.
Preferably, the compound no zinc-type shop primer, wherein the B component is made by the following method:
The ethyl polysilicate that degree of hydrolysis is 48-52%, dioxide-containing silica is 40-42% is put into reaction kettle, is stirred
It mixes and is warming up to 45-50 DEG C, polyurethane-modified dose is pumped into high-order dropwise adding tank, start to be added dropwise polyurethane-modified dose, control 1 hour
Be added dropwise, keep be added dropwise when temperature be no more than 70 DEG C, after being added dropwise 70 DEG C heat preservation 45-60 minutes, be then cooled to
50 DEG C hereinafter, filling and sealing is spare.
Preferably, the compound no zinc-type shop primer, wherein described polyurethane-modified dose is 48- with degree of hydrolysis
52%, the weight ratio for the ethyl polysilicate that dioxide-containing silica is 40-42% is 1.3-1.6: 1.
Preferably, the compound no zinc-type shop primer, wherein described polyurethane-modified dose is made by the following method
:
By the mixed with propylene glycol of the acetic anhydride butyl ester of 12-18 parts by weight and 10-15 parts by weight, propylene glycol-acetic acid is obtained
Propylene glycol-butyl acetate solution is added in high-order dropping bath by butyl acetate solution；By the acetic anhydride butyl ester of 38-52 parts by weight
In the toluene di-isocyanate(TDI)s of 25-30 parts by weight investment reaction kettle, stirring is warming up to 40-45 DEG C, then begins to be added dropwise the third two
Alcohol-butyl acetate solution, has dropped evenly in 1.5-2h, starts simultaneously at uniform heating when starting and being added dropwise, until dripping
Shi Wendu rises to 68-72 DEG C just, and is kept for 50-70 minutes at this temperature, continues thereafter with and is warming up to 74-76 DEG C and herein temperature
Degree lower heat preservation 50-70 minutes, nco value is then measured by sampling, when nco value reaches 7.2-7.3%, is cooled to 50 DEG C hereinafter, filling
Dress sealing is spare.
Preferably, the compound no zinc-type shop primer, wherein the degree of hydrolysis is 48-52%, silica contains
Amount is that the ethyl polysilicate of 40-42% is made by the following method:
The acidifying water of 3-7 parts by weight is placed in high-order dropwise adding tank, is 40-42% by 3-7 parts by weight of silica content
Ethyl polysilicate and the dehydrated alcohols of 50-70 parts by weight be added in reaction kettle, stir, be warming up to 58-62 DEG C, start to be added dropwise
Acidifying water drips for 1 hour, then raises temperature to 68-72 DEG C, after keeping the temperature 1.5-2h, terminal is measured with morpholine, when control is gelled
Between in 150-350s, the ethyl polysilicate that obtained degree of hydrolysis is 48-52%, dioxide-containing silica is 40-42%.
Preferably, the compound no zinc-type shop primer, wherein the acidifying water is 36% technical hydrochloric acid: ice vinegar
The pH value of acid=4: 1 weight ratios is the aqueous solution of 2-3.
Preferably, the compound no zinc-type shop primer, wherein the polyamide wax pulp includes: rilanit special
Modified polyamide wax powder, polyamide wax powder and polyamide wax antisettling agent.
The beneficial effects of the present invention are:
1) problem low for partial hydrolystate solid content, this case redesign formula, improve partial hydrolysis silicic acid
The solid content of ethyl ester；
2) base-material of the ethyl orthosilicate partial hydrolystate as inorganic silicic acid spelter coating is traditionally used, ethyl orthosilicate
Molecular weight is 208.3275, uses raw material of the ethyl polysilicate as partial hydrolystate, the poly- silicon of 40-42% dioxide-containing silica instead
The molecular weight of acetoacetic ester is generally 880-1000, improves its adhesiveness and flexibility；
3) the polyurethane adducts modified polysilicate ethyl ester fraction hydrolysis with the better polyalcohol of waterproof anti-permeability is used
Object improves the adhesive force, moisture penetration and fastness of film forming matter.
Specific embodiment
The present invention will be further described in detail below with reference to the embodiments, to enable those skilled in the art referring to specification
Text can be implemented accordingly.
Example 1 prepares a kind of polyurethane-modified inorganic shop primer without zinc
1. preparing the polyurethane-modified inorganic shop primer B component without zinc first
(1) polyurethane-modified dose is prepared
A. it determines consisting of: 10~15 parts by weight of propylene glycol, 25~30 parts by weight of toluene di-isocyanate(TDI) (TDI), nothing
50~70 parts by weight of water acetic acid butyl ester are formed, and non-volatile part is polyurethane-modified dose of 34~36%.
B. polyurethane-modified dose of preparation method and step:
It is prepared in accordance with the following methods with step:
The acetic anhydride butyl ester of formula ratio 1/4 is added to the container, the propylene glycol of formula ratio is added, is placed in high-order dropping liquid
In slot；By in the acetic anhydride butyl ester and TDI of surplus investment reaction kettle, stirring is warming up to 40~45 DEG C, starts to be added dropwise the third two
Alcohol-butyl acetate solution, has dropped evenly in 1.5~2h, uniformly heats up, and the temperature dripped rises to 68~72 DEG C, and
It is kept for 50~70 minutes at a temperature of this, then is warming up to 74~76 DEG C and keeps the temperature 50~70 minutes, nco value is measured by sampling and reaches theoretical value
When 7.2~7.3%, 50 DEG C are cooled to hereinafter, filling and sealing is spare.
(2) preparation of 50% hydrolysate of ethyl polysilicate
A. the composition of 50% hydrolysate of ethyl polysilicate
35~40 weight of ethyl polysilicate that 50% hydrolysate of ethyl polysilicate is 40~42% by dioxide-containing silica
Part, 3~7 parts by weight of acidifying water, 50~70 parts by weight of dehydrated alcohol are formed.
B. 50% hydrolysate preparation method of ethyl polysilicate and step
It is prepared according to the following steps with method:
With 36% technical hydrochloric acid: glacial acetic acid=4:1 weight ratio mixed solution, the deionized water that adjustment pH value is 2~3,
As acidifying water.
The acidifying water of formula ratio is placed in high-order dropwise adding tank, industrial ethyl polysilicate, the dehydrated alcohol of formula ratio, is added
Enter into reaction kettle, start stirring, be warming up to (60 ± 2) DEG C, starts to drop evenly acidifying water, drip within 1 hour, then heat up
To (70 ± 2) DEG C, after keeping the temperature 1.5~2h, terminal is measured with Ma beautiful jade reagent, gelling time is controlled in 150~350s, is prepared into water
Xie Du is 48~52%, the ethyl polysilicate partial hydrolystate that non-volatile part is 34~36%.
Reaction end measurement:
The hydrolysis ethyl polysilicate of 4.5ml is added in graduated 10ml scale test tube, 0.5ml morpholine is then added,
By the positive and negative shake of test tube, its gelling time is measured, general control is qualified between 150~350s at 25 DEG C.
50% degree of hydrolysis product technology data of ethyl polysilicate:
The product data of 2 ethyl polysilicate of table, 50% hydrolysate
| Project | Index |
| Solid content % | 33~37 |
| Density g/cm3 | 0.90~1.00 |
| Viscosity applies -4/25 DEG C, s | 25~50 |
| Morpholine test, s | 150~350 |
| Storage stability | Do not change within 6 months |
(3) polyurethane-modified dose of modified polysilicate ethyl ester fraction hydrolysate preparation of
A. the composition of polyurethane-modified ethyl polysilicate partial hydrolystate
Consisting of 100 parts by weight of ethyl polysilicate partial hydrolystate, polyurethane-modified dose of 130~160 parts by weight.
B. polyurethane-modified ethyl polysilicate partial hydrolystate preparation method and step
It is prepared in accordance with the following methods with step:
First ethyl polysilicate partial hydrolystate is squeezed into high-order dropping bath；Reaction kettle is put by polyurethane-modified dose
In, 45~50 DEG C are heated to, starts that ethyl polysilicate partial hydrolystate solution is added dropwise, drips within 60~70 minutes, when being added dropwise
Heating, after dropwise addition temperature be no more than 70 DEG C, more than when cool down, drip after 70~75 DEG C keep the temperature 1~1.5 hour, be measured by sampling
When nco value is 0.5~0%, 50 DEG C are cooled to hereinafter, filling and sealing is spare.
The above are B components.
2. the not polyurethane-modified inorganic compounding shop primer component A preparation of zincilate
Component A is carried out according to formula as below:
The polyurethane-modified inorganic compounding shop primer list of ingredients of the not zincilate of table 3
| Raw material | Wt% |
| Component A polyvinyl butyral 10 seconds | 2~4 |
| Polyamide wax pulp 20% | 0.3~0.6 |
| Butanol | 5~9 |
| Dehydrated alcohol | 15~17 |
| Meet phosphorus titanium valve | 7~10 |
| Ferrophosphorus powder | 35~45 |
| It is total | 80 |
Preparation method and step: first in dehydrated alcohol and butanol the investment container of formula ratio, starting high speed disperser, with
300~500r/min is stirred at low speed, and is sprinkled into polyvinyl butyral, is spread after reuniting vinyl butyral, and speed-raising to 700~
1000r/min is sufficiently uniformly dissolved polyvinyl butyral, then put into formula ratio polyamide wax pulp, step by step input its
Remaining phosphorus titanium valve and ferrophosphorus powder, after feeding intake, 1400r/min is arrived in speed-raising, high speed dispersion 30~50 minutes, filling to make
For component A product.
The polyurethane-modified ethyl polysilicate of B component
Partial hydrolystate 35% 20
Total 100.0
The organic-inorganic composite shop primer film performance of the present invention not zincilate
The not zincilate organic-inorganic composite shop primer film performance of table 4
Product of the present invention and other traditional coating performance comparisons, are shown in Table 5.
5 invention product of table is compared with traditional product performance
As can be drawn from Table 5, it was concluded that
1. using ethyl polysilicate hydrolysis 50%, preparation not zincilate shop primer, film forming obviously than
Want excellent more using traditional teos hydrolysis degree 25%；
2. polyurethane-modified 50% degree of hydrolysis of ethyl polysilicate is used, the shop primer of the not zincilate of preparation,
Resistance to salt water and weatherability have all reached the shop primer of the pure zinc powder of non-modified 50% degree of hydrolysis of ethyl polysilicate；
3. polyurethane-modified ethyl polysilicate partial hydrolystate, substantially increases water resistance and corrosion resistance；
4. passing through actual application, this technology and product have all obtained good verifying, it was demonstrated that this technology is mature
, good Social benefit and economic benefit can will be obtained to marketing.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and embodiment shown here.
Claims (9)
1. a kind of organic-inorganic composite shop primer of not zincilate, it is characterized in that being made of component A and B component, component A is
By 3.0~5.0 parts by weight of polyvinyl butyral, 0.3~0.6 parts by weight of polyamide wax pulp, 15~17.0 weight of dehydrated alcohol
Part, 5~9 parts by weight of butanol, 7~10 parts by weight of phosphorus titanium valve, 35~45 parts by weight of ferrophosphorus powder composition, component A total amount is 80 weight
Part；B component is 20 weight of ethyl polysilicate of 40~42% dioxide-containing silicas of polyurethane-modified dose of 50% modified degree of hydrolysis
Measure part.
2. the organic-inorganic composite shop primer of not zincilate as described in claim 1, it is characterized in that B component is by polyurethane
100 parts of 50% hydrolysate of ethyl polysilicate of 130~160 parts by weight of modifying agent and 40~42% dioxide-containing silicas is formed.
3. the organic-inorganic composite shop primer of not zincilate as claimed in claim 2, characterized in that polyurethane-modified dose
The ethyl polysilicate of 40~42% dioxide-containing silicas of 50% modified degree of hydrolysis the preparation method comprises the following steps: by 50% degree of hydrolysis
The ethyl polysilicate of 40~42% dioxide-containing silicas is put into reaction kettle, and stirring is warming up to 45~50 DEG C, and polyurethane is changed
Property agent squeeze into high-order dropwise adding tank, start to be added dropwise polyurethane-modified dose, drip within about 1 hour, keep dropping temperature be no more than 70
DEG C, more than when cool down, drip after 70 DEG C keep the temperature 45~60 minutes, be cooled to 50 DEG C hereinafter, filling and sealing is spare.
4. the organic-inorganic composite shop primer of not zincilate as claimed in claim 3, characterized in that polyurethane-modified dose
By 10~15 parts by weight of propylene glycol, 25~30 parts by weight of toluene di-isocyanate(TDI) (TDI), 50~70 parts by weight of acetic anhydride butyl ester
It is formed.
5. the organic-inorganic composite shop primer of not zincilate as claimed in claim 3, characterized in that polyurethane-modified dose
The preparation method comprises the following steps: the acetic anhydride butyl ester of formula ratio 1/4 is added to the container, add the propylene glycol of formula ratio, merging is high
In the dropping bath of position；By in acetic anhydride butyl ester and TDI the investment reaction kettle of surplus, stirring is warming up to 40~45 DEG C, starts to drip
Add propylene glycol-butyl acetate solution, dropped evenly in 1.5~2h, uniformly heated up, the temperature dripped rises to 68~72
DEG C, and kept for 50~70 minutes at this temperature, then be warming up to 74~76 DEG C and keep the temperature 50~70 minutes, nco value is measured by sampling and reaches
When to theoretical value 7.2~7.3%, 50 DEG C are cooled to hereinafter, filling and sealing is spare.
6. the organic-inorganic composite shop primer of not zincilate as claimed in claim 3, characterized in that 50% degree of hydrolysis
35~40 weight of ethyl polysilicate that the ethyl polysilicate of 40~42% dioxide-containing silicas is 40~42% by dioxide-containing silica
Part, 3~7 parts by weight of acidifying water are measured, 50~70 parts by weight of dehydrated alcohol are formed.
7. the organic-inorganic composite shop primer of not zincilate as claimed in claim 6, characterized in that 50% degree of hydrolysis
The ethyl polysilicate of 40~42% dioxide-containing silicas the preparation method comprises the following steps: the acidifying water of formula ratio is placed in high-order dropwise adding tank
In, it industrial ethyl polysilicate, the dehydrated alcohol of formula ratio, is added in reaction kettle, starts stirring, be warming up to (60 ± 2) DEG C,
Start to drop evenly acidifying water, drip within 1 hour, be then warming up to (70 ± 2) DEG C, after keeping the temperature 1.5~2h, is surveyed with Ma beautiful jade reagent
Determine terminal, for control gelling time in 150~350s, being prepared into degree of hydrolysis is 48~52%, non-volatile part be 34~36% it is poly-
Silester partial hydrolystate.
8. the organic-inorganic composite shop primer of not zincilate as claimed in claim 6, characterized in that the preparation of acidifying water
Method are as follows: with 36% technical hydrochloric acid: glacial acetic acid=4:1 weight ratio mixed solution, the deionized water that adjustment pH value is 2~3 are made
For acidifying water.
9. the organic-inorganic composite shop primer of not zincilate as described in claim 1, characterized in that poly- in component A
Amide wax liquor, comprising the castor oil modified polyamide wax powder after overactivation with good thixotropic property, polyamide wax pulp gathers
Amide waxe anti-settling agent.
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| CN201710013457.XA CN107011791B (en) | 2017-01-09 | 2017-01-09 | A kind of organic-inorganic composite shop primer of not zincilate and preparation method thereof |
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| CN201710013457.XA CN107011791B (en) | 2017-01-09 | 2017-01-09 | A kind of organic-inorganic composite shop primer of not zincilate and preparation method thereof |
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| CN112791686B (en) * | 2021-01-06 | 2022-11-15 | 安徽汇利涂料科技有限公司 | Preparation method of epoxy zinc-rich primer base material |
| CN114773990B (en) * | 2022-03-10 | 2023-01-06 | 北京东方雨虹防水技术股份有限公司 | Alcohol-soluble inorganic zinc-rich primer and preparation method thereof |
| CN114644339B (en) * | 2022-04-29 | 2023-04-25 | 成都理工大学 | Method for removing impurities in silicon by adopting inorganic zinc salt |
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|---|---|---|---|---|
| JP2005324361A (en) * | 2004-05-12 | 2005-11-24 | Dainippon Printing Co Ltd | Barrier film and laminated material using it |
| CN102260423A (en) * | 2011-07-18 | 2011-11-30 | 苏州吉人漆业有限公司 | Alcohol-soluble phosphate high temperature resistant long-acting anti-corrosive paint and preparation method thereof |
| CN102993859A (en) * | 2012-11-28 | 2013-03-27 | 天长市开林化工有限公司 | Zinc powder-free shop primer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7732552B2 (en) * | 2006-01-27 | 2010-06-08 | Momentive Performance Materials Inc. | Low VOC epoxy silane oligomer and compositions containing same |
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2017
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| JP2005324361A (en) * | 2004-05-12 | 2005-11-24 | Dainippon Printing Co Ltd | Barrier film and laminated material using it |
| CN102260423A (en) * | 2011-07-18 | 2011-11-30 | 苏州吉人漆业有限公司 | Alcohol-soluble phosphate high temperature resistant long-acting anti-corrosive paint and preparation method thereof |
| CN102993859A (en) * | 2012-11-28 | 2013-03-27 | 天长市开林化工有限公司 | Zinc powder-free shop primer and preparation method thereof |
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