CN104087148B - High-strength polyurethane waterproof coating material - Google Patents
High-strength polyurethane waterproof coating material Download PDFInfo
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Abstract
The invention discloses a kind of high-strength polyurethane waterproof coating material, including component A and B component, be the proportioning mix homogeneously of 2: 1 by weight by component A, B component during use；Described component A is made up of following raw material: trifunctional polyether polyol, two functional polyethers polyhydric alcohol, terminal hydroxy group phthalic acid polyol oligomer, chlorination MDA cross-linking agent, ferric oxide red colorant, wollastonite packing, calcium oxide filler, pearl filler, the plasticizer of 80～100 parts, antioxidant 264, liquid and/or solid-state coumarone indene resin, silane defoamer；Described B component is made up of following raw material: trifunctional polyether polyol, two functional polyethers polyhydric alcohol, benzoic acid polyol ester plasticizer, isomerization methyl diphenylene diisocyanate.Polyurethane water-proof paint of the present invention, has the features such as high tensile, high fracture elongation, tear-resistant, waterproof, wet and heat ageing resistant, resistance to chemical attack and cost be relatively low, and the railway concrete bridge floor being particularly well-suited to requirement of strength high is waterproof.
Description
Technical field
The present invention relates to the waterproof material of a kind of organic high molecular compound and inorganic fillings composition
Material, particularly relates to a kind of high-strength polyurethane waterproof coating material, is particularly suited for requirement of strength high
Railway concrete bridge floor waterproof.
Background technology
Polyurethane water-proof paint has good elasticity, sealing, chemical resistance, in work
Industry is widely used with civil buildings waterproof field.Original polyurethane water-proof paint is adopted mostly
It is that raw material forms prepolymer with polyether reactant with the toluene di-isocyanate(TDI) that toxicity is higher, as anti-
The main component of water paint.The high toxicity of toluene di-isocyanate(TDI) is except bringing coating production process
In to the health effect of operator outside, it is also possible to bring coating use process user is good for
Health affects, and therefore must assure that in water-repellent paint production process without having neither part nor lot in the free different of reaction
Cyanate exists.In order to reduce free isocyanide acid number, the hydroxyl group when carrying out Isocyanate prepolymers
Divide and must have certain excess than theoretical amount, so cause prepolymer product certainly will have moieties amount
Bigger prepolymer exists, and makes dope viscosity increase.In order to ensure the construction technology of coating,
Generally require interpolation substantial amounts of solvent such as dimethylbenzene, tar equal solvent to reduce viscosity.Solvent
Add, also bring with environment accumulating hidden with the safety of use process work progress is the most unhealthful
Suffering from, it evaporate into atmospheric environment and also brings waste economically.The most original polyurethane is prevented
Water paint low strength, if GB/T19250-2003 is to film hot strength requirement >=2.45Mpa,
And railway deck water-repellent paint standard TB/T2965-2011 requirement >=6.0Mpa, it is clear that Yuan Youguo
Mark product can not meet Iron-surfur clusters requirement.In order to solve above-mentioned two large problems, people are carried out
A lot of improve, such as CN201010545081, CN200810018411, CN200910069936,
CN201310199705, CN200710119994, CN200910014090,
CN201010138301, CN201210286027 etc. propose to use hypotoxic two amido hexichol
Methane diisocyanate substitutes highly toxic toluene di-isocyanate(TDI), uses phthalic acid two fourth
(pungent) ester, chlorinated paraffin, Petropols are as dilution or plasticizer, though said method can make
The bigger reduction of water-repellent paint toxicity, safety in utilization increases, and water-repellent paint intensity the most substantially can
Reach Iron-surfur clusters requirement, but the stability of product and economic aspect still suffer from deficiency, need into
One step is improved and improves.
Summary of the invention
It is an object of the invention to provide a kind of high-strength polyurethane waterproof coating material, it has height and draws
Stretch intensity, high fracture elongation, tear-resistant, waterproof, wet and heat ageing resistant, resistance to chemical attack
And the feature such as cost is relatively low, the railway concrete bridge floor being particularly well-suited to requirement of strength high is waterproof.
For achieving the above object, the technical scheme is that a kind of high-strength polyurethane of design is prevented
Water paint, including component A and B component, during use by described component A, B component by weight
It is the proportioning mix homogeneously of 2: 1, brushes and needing waterproof surface of concrete；
Described component A is made up of the raw material of following weight portion: the hydroxyl value of 100 parts
The trifunctional polyether polyol of 30～60mgKOH/g, the hydroxyl value of 20～30 parts
The two functional polyethers polyhydric alcohol of 56～280mgKOH/g, the hydroxyl value of 10～20 parts
The terminal hydroxy group phthalic acid polyol oligomer of 280～400mgKOH/g, the chlorination of 30～50 parts
MDA cross-linking agent, the 300～2000 mesh ferric oxide red colorants of 8～10 parts, 10～20
200～the 2000 mesh wollastonite packings of part, the 200～2000 mesh calcium oxide filler of 5～10 parts,
200～the 2000 mesh pearl fillers of 100～200 parts, the plasticizer of 80～100 parts, 0.5～1 part
Antioxidant 264, the liquid of 60～80 parts and/or solid-state coumarone indene resin, the silane of 0.1～0.5 part
Defoamer；During plasticizer is chlorinated paraffin 42, chlorinated paraffin 70 in described component A one
Plant or two kinds；
Described B component is made up of the raw material of following weight portion: the hydroxyl value of 40～80 parts
The trifunctional polyether polyol of 30～60mgKOH/g, the hydroxyl value 56～112mgKOH/g of 150 parts
Two functional polyethers polyhydric alcohol, the benzoic acid polyol ester plasticizer of 60～100 parts, 95～150
The isomerization methyl diphenylene diisocyanate of part.
Preferably, described component A is prepared via a method which: get the raw materials ready according to weight portion；By three
Functional polyethers polyhydric alcohol, two functional polyethers polyhydric alcohol, terminal hydroxy group phthalic acid polyol oligomer,
Chlorination MDA cross-linking agent is mixed is incorporated in 100～130 DEG C of dissolvings 0.5～1 hour, then adds
Enter ferric oxide red colorant, wollastonite, calcium oxide, calcium carbonate, plasticizer, antioxidant 264,
Liquid and/or solid-state coumarone indene resin, mix and be incorporated in 100～120 DEG C ,-0.09～0.10Mpa dehydration
1～3 hour, it is cooled to 60～80 DEG C, adds silane defoamer, grind through three rollers or colloid mill and divide
Shed material, detection hydroxyl value 45～65mgKOH/g, 25 DEG C of viscosity 10000～30000mpa.s,
As component A.
Preferably, described B component is prepared via a method which: get the raw materials ready according to weight portion；By three
Functional polyethers polyhydric alcohol, two functional polyethers polyhydric alcohol, benzoic acid polyol ester are mixed to be incorporated in
100～130 DEG C ,-0.09～0.10Mpa dehydration 1～2 hour, it is cooled to 60～80 DEG C, adds isomery
Change methyl diphenylene diisocyanate to react 2～4 hours, be cooled to 40～60 DEG C of dischargings, detection
NCO content is 8%～10%, 25 DEG C of viscosity 2000～5000mpa.s, as B component.
Advantages of the present invention and having the beneficial effects that: a kind of waterproof painting of high-strength polyurethane is provided
Material, it has high tensile, high fracture elongation, tear-resistant, waterproof, wet-heat resisting is old
The features such as change, resistance to chemical attack and cost are relatively low, are particularly well-suited to the high railway of requirement of strength and mix
Solidifying soil bridge deck water-proof.
The present invention has a characteristic that
1, component A firming agent prepare in introduce rigidity is better than polyether polyol, price is lower
Phthalic acid and polyhydric alcohol (such as dihydroxylic alcohols) oligomer substitute the polyether polyol of pure fat chain,
Be conducive to improving water-repellent paint hot strength.
2, use the benzoic acid polyol ester that molecular weight is bigger, substitute the O-phthalic of little molecule
Dibutyl phthalate, decreases may migrating of plasticizer；With solid ancient marlon resin and liquid Gu horse
Grand resin is arranged in pairs or groups, and substitutes C5 Petropols and partial oxidation paraffin 70, makes the toughness of film more
Good.
3, using mixed fillers, wollastonite, calcium oxide, calcium carbonate different proportion are taken with fineness
Join, and by suitable grinding distribution, make the existing relatively low viscosity of coating be easy to construction, the most unlikely
Lump in making filling settlement.
4, rationally assembling by two functional polyethers and trifunctional polyethers in B component preparation, guarantor
Card hot strength and the balance of elongation percentage.
Detailed description of the invention
Below in conjunction with embodiment, the detailed description of the invention of the present invention is further described.Below
Embodiment is only used for clearly illustrating technical scheme, and can not limit with this
Protection scope of the present invention.
The technical scheme that the present invention implements is:
By the trifunctional polyether polyol of the hydroxyl value 30～60mgKOH/g of 100 parts, 20～30 parts
Two functional polyethers polyhydric alcohol of hydroxyl value 56～280mgKOH/g, the hydroxyl value of 10～20 parts
The terminal hydroxy group phthalic acid polyol oligomer of 280～400mgKOH/g, the chlorination of 30～50 parts
MDA cross-linking agent, mixes and is incorporated in 100～130 DEG C of dissolvings 0.5～1 hour；Add
300～the 2000 mesh ferric oxide red colorants of 8～10 parts, the 200～2000 mesh wollastonites of 10～20 parts are filled out
Material, the 200～2000 mesh calcium oxide filler of 5～10 parts, the 200～2000 mesh carbonic acid of 100～200 parts
Calcium filler, (plasticizer is in chlorinated paraffin 42, chlorinated paraffin 70 to the plasticizer of 80～100 parts
One or both), the antioxidant 264 of 0.5～1 part, the liquid of 60～80 parts and/or solid-state coumarone
Resin, mixes and is incorporated in 100～120 DEG C ,-0.09～0.10Mpa dehydration 1～3 hour, is cooled to 60～80
DEG C, add the silane defoamer of 0.1～0.5 part, through three rollers or colloid mill grinding distribution discharging, inspection
Survey hydroxyl value is 45～65mgKOH/g, 25 DEG C of viscosity 10000～30000mpa.s, as component A.
By the trifunctional polyether polyol of the hydroxyl value 30～60mgKOH/g of 40～80 parts, 150 parts
Two functional polyethers polyhydric alcohol of hydroxyl value 56～112mgKOH/g, the benzoic acid of 60～100 parts is polynary
Alcohol ester plasticiser, mixes and is incorporated in 100～130 DEG C ,-0.09～0.10Mpa dehydration 1～2 hour, fall
Temperature, to 60～80 DEG C, adds the isomerization methyl diphenylene diisocyanate reaction 2～4 of 95～150 parts
Hour, it being cooled to 40～60 DEG C of dischargings, detection NCO content is 8%～10%, 25 DEG C of viscosity
2000～5000mpa.s, as B component.
It is the proportioning mix homogeneously of 2: 1 by weight by described component A, B component during use, is coated with
Brush and needing waterproof surface of concrete.
Specific embodiment is as follows:
Embodiment 1
Putting into trifunctional polyethers 330N (hydroxyl value 36) 100kg at 500L reactor, two senses are gathered
Ether 220 (hydroxyl value 56) 25kg, the low condensation polymer of terminal hydroxy group phthalic acid polyhydric alcohol (hydroxyl value 400)
15kg, chlorination MDA cross-linking agent 45kg, stirring is warming up to 110～120 DEG C of maintenances
0.5 hour；Add 300 mesh ferric oxide red colorant 9kg, 400 mesh wollastonite packing 15kg, 200
Mesh calcium oxide filler 5kg, 600 mesh pearl filler 180kg, chlorinated paraffin 42 is 85kg, anti-
Oxygen agent 264 is 1kg, liquid coumarone indene resin 50kg, solid-state coumarone indene resin 10kg,
110～120 DEG C ,-0.09～0.10MPa vacuum stirring mixed dehydration 2 hours, it is cooled to 60 DEG C,
Add silane defoamer 0.4kg, grind discharging through colloid mill, test 25 DEG C of viscosity 15100mpa.s,
Hydroxyl value 54.8mgKOH/g, packaging is as component A.
Trifunctional polyethers 330 (hydroxyl value 56) 80kg, two functional polyethers are put at 500L reactor
220 (hydroxyl value 56) 150kg, benzoic acid polyol ester 100kg, at 100～110 DEG C,
-0.09～0.10MPa vacuum stirring dehydration and low boilers 2 hours, is cooled to 60～70 DEG C, adds
Entering isomerization '-diphenylmethane diisocyanate Bayer2460M is 150kg, 70～80 DEG C of maintenances
Reacting 3 hours, be cooled to 40～60 DEG C of dischargings, test 25 DEG C of viscosity 3620mpa.s, NCO contains
Amount 8.50%, packaging is as B component.
Taking above-mentioned component A 300g, B component 150g stirs 3～5 minutes in mixed at room temperature, presses
GB/T19250～2003 methods prepare coated film sample maintenance, and maintenance carries out performance survey after terminating
Examination also requires index contrast as shown in table 1 with GB and Ministry of Railways TB/T2965～2011.
Table 1 embodiment 1 high-strength polyurethane waterproof coating material the performance test results
Embodiment 2
Trifunctional polyether polyol (hydroxyl value 30) 100kg, two senses are put at 500L reactor
Polyether polyol (hydroxyl value 120) 20kg, terminal hydroxy group phthalic acid polyhydric alcohol low condensation polymer (hydroxyl
Value 300) 10kg, chlorination MDA cross-linking agent 30kg, stirring is warming up to 110～120
DEG C maintain 0.5 hour；Add 1000 mesh ferric oxide red colorant 8kg, 200 mesh wollastonite packings
10kg, 1000 mesh calcium oxide filler 7kg, 200 mesh pearl filler 100kg, chlorinated paraffin 70
For 80kg, antioxidant 264 is 0.5kg, liquid coumarone indene resin 80kg, at 100 DEG C, and-0.09MPa
Vacuum stirring mixed dehydration 3 hours, is cooled to 60 DEG C, adds silane defoamer 0.1kg, through glue
Body barreling grinds material, tests 25 DEG C of viscosity 10000mpa.s, hydroxyl value 45mgKOH/g, and packaging is made
For component A.
Putting into trifunctional polyether polyol (hydroxyl value 30) 40kg at 500L reactor, two senses are gathered
Ethoxylated polyhydric alcohol (hydroxyl value 70) 150kg, benzoic acid polyol ester 60kg, at 100 DEG C ,-0.09MPa
Vacuum stirring dehydration and low boilers 1 hour, be cooled to 60 DEG C, adds isomerization diphenyl-methane
Diisocyanate B ayer2460M is 95kg, maintains reaction 2 hours at 70 DEG C, is cooled to 40 DEG C
Discharging, tests 25 DEG C of viscosity 2000mpa.s, NCO content 8%, and packaging is as B component.
It is the proportioning mix homogeneously of 2: 1 by weight by described component A, B component during use, is coated with
Brush and needing waterproof surface of concrete.
Embodiment 3
Trifunctional polyether polyol (hydroxyl value 60) 100kg, two senses are put at 500L reactor
Polyether polyol (hydroxyl value 280) 30kg, terminal hydroxy group phthalic acid polyhydric alcohol low condensation polymer (hydroxyl
Value 280) 20kg, chlorination MDA cross-linking agent 50kg, stirring is warming up to 120 DEG C of dimensions
Hold 0.5 hour；Add 2000 mesh ferric oxide red colorant 10kg, 2000 mesh wollastonite packings
20kg, 2000 mesh calcium oxide filler 10kg, 2000 mesh pearl filler 200kg, chlorinated paraffin
42 is 85kg, and chlorinated paraffin 70 is 15kg, and antioxidant 264 is 0.7kg, solid-state coumarone indene resin
70kg, at 120 DEG C, 0.10MPa vacuum stirring mixed dehydration 1 hour, it is cooled to 80 DEG C, adds
Enter silane defoamer 0.5kg, grind discharging through colloid mill, test 25 DEG C of viscosity 30000mpa.s,
Hydroxyl value 65mgKOH/g, packaging is as component A.
Putting into trifunctional polyether polyol (hydroxyl value 60) 60kg at 500L reactor, two senses are gathered
Ethoxylated polyhydric alcohol (hydroxyl value 112) 150kg, benzoic acid polyol ester 80kg, at 130 DEG C, 0.10MPa
Vacuum stirring dehydration and low boilers 1.5 hours, be cooled to 80 DEG C, adds isomerization hexichol first
Alkane diisocyanate B ayer2460M is 120kg, maintains reaction 4 hours at 80 DEG C, is cooled to
60 DEG C of dischargings, test 25 DEG C of viscosity 5000mpa.s, NCO content 10%, and packaging is as B component.
It is the proportioning mix homogeneously of 2: 1 by weight by described component A, B component during use, is coated with
Brush and needing waterproof surface of concrete.
The present invention also provides for comparative example 1-7, and its proportioning is as shown in table 2.
The proportioning of table 2 comparative example 1-7
The film performance test of comparative example 1-7 is as shown in table 3.
The film performance test and comparison of table 3 comparative example 1-7
Comparative example 1, comparative example 2 and comparative example 3, polyurethane water-proof paint preparation method is with implementing
Example 1, only changes component A composition of raw materials middle-end hydroxy benzenes dioctyl phthalate polyhydric alcohol low-shrinkage copolymer content
With hydroxyl value, obtained A, B component index change such as table 2, prepared film performance test result
Relatively such as table 3.Comparative example 2, beyond the scope of the invention, is added without terminal hydroxy group phthalic acid polyhydric alcohol
Low condensation polymer, gained film hot strength is less than ferrum mark required value.
Comparative example 4 and comparative example 5, polyurethane water-proof paint preparation method, with embodiment 1, only changes
Becoming solid-state and liquid coumarone indene resin content in component A composition of raw materials, obtained A, B component refer to
Mark change such as table 2, prepared film performance test result compares such as table 3.Comparative example 4 and comparing
Example 5 changes coumarone indene resin addition but still in application claims scope, though result intensity
Change but still conform to ferrum mark requirement.
Comparative example 6 and comparative example 7, polyurethane water-proof paint preparation method, with embodiment 1, only changes
Becoming two functional polyethers and the ratio of trifunctional polyethers in B component, obtained A, B component index become
Changing such as table 2, prepared film performance test result compares such as table 3.Comparative example 6 trifunctional polyethers
Content height exceeds the scope of the invention, though gained film hot strength is high but elongation percentage is on the low side；Otherwise,
Comparative example 7 trifunctional polyethers is on the low side, beyond the scope of the invention, though elongation percentage is high hot strength
On the low side.
The above is only the preferred embodiment of the present invention, it is noted that lead for this technology
For the those of ordinary skill in territory, on the premise of without departing from the technology of the present invention principle, it is also possible to
Making some improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (1)
1. high-strength polyurethane waterproof coating material, it is characterised in that include component A and B component,
It is the proportioning mix homogeneously of 2: 1 by weight by described component A, B component during use；
Described component A is made up of the raw material of following weight portion: the hydroxyl value of 100 parts
The trifunctional polyether polyol of 30～60mgKOH/g, the hydroxyl value of 20～30 parts
The two functional polyethers polyhydric alcohol of 56～280mgKOH/g, the hydroxyl value of 10～20 parts
The terminal hydroxy group phthalic acid polyol oligomer of 280～400mgKOH/g, the chlorination of 30～50 parts
MDA cross-linking agent, the 300～2000 mesh ferric oxide red colorants of 8～10 parts, 10～20
200～the 2000 mesh wollastonite packings of part, the 200～2000 mesh calcium oxide filler of 5～10 parts,
200～the 2000 mesh pearl fillers of 100～200 parts, the plasticizer of 80～100 parts, 0.5～1 part
Antioxidant 264, the liquid of 60～80 parts and/or solid-state coumarone indene resin, the silane of 0.1～0.5 part
Defoamer；During plasticizer is chlorinated paraffin 42, chlorinated paraffin 70 in described component A one
Plant or two kinds；
Described B component is made up of the raw material of following weight portion: the hydroxyl value of 40～80 parts
The trifunctional polyether polyol of 30～60mgKOH/g, the hydroxyl value 56～112mgKOH/g of 150 parts
Two functional polyethers polyhydric alcohol, the benzoic acid polyol ester plasticizer of 60～100 parts, 95～150
The isomerization methyl diphenylene diisocyanate of part；
Described component A is prepared via a method which: get the raw materials ready according to weight portion；By trifunctional polyethers
Polyhydric alcohol, two functional polyethers polyhydric alcohol, terminal hydroxy group phthalic acid polyol oligomer, chlorination two
Diaminodiphenylmethane cross-linking agent is mixed is incorporated in 100～130 DEG C of dissolvings 0.5～1 hour, adds oxidation
Iron oxide red pigment, wollastonite, calcium oxide, calcium carbonate, plasticizer, antioxidant 264, liquid and/
Or solid-state coumarone indene resin, mixing and be incorporated in 100～120 DEG C ,-0.09～0.10Mpa dehydration 1～3 is little
Time, it is cooled to 60～80 DEG C, adds silane defoamer, go out through three rollers or colloid mill grinding distribution
Material, detection hydroxyl value 45～65mgKOH/g, 25 DEG C of viscosity 10000～30000mpa.s, as
Component A；
Described B component is prepared via a method which: get the raw materials ready according to weight portion；By trifunctional polyethers
Polyhydric alcohol, two functional polyethers polyhydric alcohol, benzoic acid polyol ester are mixed is incorporated in 100～130 DEG C,
-0.09～0.10Mpa dehydration 1～2 hour, is cooled to 60～80 DEG C, adds isomerization diphenylmethyl
Alkane di-isocyanate reaction 2～4 hours, be cooled to 40～60 DEG C of dischargings, and detection NCO content exists
8%～10%, 25 DEG C of viscosity 2000～5000mpa.s, as B component.
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| CN105038685A (en) * | 2015-08-14 | 2015-11-11 | 上海应用技术学院 | Non-tar cable connector polyurethane waterproof sealant and preparation method thereof |
| CN105461880A (en) * | 2015-11-20 | 2016-04-06 | 嘉兴洛克化学工业有限公司 | Superhigh-modulus resin used for fiber waterproof coatings and preparing method thereof |
| CN105505184A (en) * | 2016-01-09 | 2016-04-20 | 安徽万诚达新型材料有限公司 | High-elasticity high weather resistance polyurethane waterproof paint for concrete bridge and preparation method thereof |
| CN105505185A (en) * | 2016-02-23 | 2016-04-20 | 安徽万诚达新型材料有限公司 | High-elasticity polyurethane waterproof paint for concrete bridges and method for preparing high-elasticity polyurethane waterproof paint |
| CN108219640A (en) * | 2018-01-26 | 2018-06-29 | 山东宏恒达防水材料工程有限公司 | It is a kind of for spraying water-repellent paint of concrete base layer and preparation method thereof |
| CN110642574A (en) * | 2019-10-22 | 2020-01-03 | 中山市武汉理工大学先进工程技术研究院 | Multi-component extrusion-injection type mortar, and preparation method and application method thereof |
| CN113956774B (en) * | 2021-09-15 | 2022-09-06 | 深圳市卓宝科技股份有限公司 | Polyurethane coating for waterproof coiled material and preparation method and application thereof |
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| JPH10218966A (en) * | 1997-02-03 | 1998-08-18 | Asahi Glass Co Ltd | Two-pack curable composition |
| CN101100582B (en) * | 2007-08-06 | 2010-10-06 | 北京东方雨虹防水技术股份有限公司 | Bi-component high-strength polyurethane waterproofing paint |
| CN101220241B (en) * | 2007-12-19 | 2011-02-09 | 上海台安工程实业有限公司 | Double-component high-strength polyurethane waterproof coating material |
| WO2011132581A1 (en) * | 2010-04-22 | 2011-10-27 | 小松精練株式会社 | Aqueous dispersion of polyurethane resin, nonporous film, and method for producing moisture-permeable waterproof fabric |
| CN102757722B (en) * | 2012-07-13 | 2014-12-10 | 江苏苏博特新材料股份有限公司 | Bi-component polyurethane coating and preparation method thereof |
| CN103436157B (en) * | 2013-07-25 | 2016-01-20 | 山东汇源建材集团有限公司 | A kind of preparation technology of high strength water crosslinking polyurethane water-proof paint |
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