CN109535385A - The preparation method of base polyurethane prepolymer for use as, preparation method and environmentally friendly polyureas sports ground surface layer - Google Patents
The preparation method of base polyurethane prepolymer for use as, preparation method and environmentally friendly polyureas sports ground surface layer Download PDFInfo
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- CN109535385A CN109535385A CN201811431415.9A CN201811431415A CN109535385A CN 109535385 A CN109535385 A CN 109535385A CN 201811431415 A CN201811431415 A CN 201811431415A CN 109535385 A CN109535385 A CN 109535385A
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- 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
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- 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
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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Abstract
The invention discloses the preparation methods of base polyurethane prepolymer for use as, preparation method and environmentally friendly polyureas sports ground surface layer, are related to polyurethane material technical field.The raw material for preparing of the base polyurethane prepolymer for use as includes 55-90 parts of polyether polyol, 10-25 parts of polyisocyanates and aliphatic or 2-6 parts of alicyclic diisocyanate；Aliphatic or alicyclic diisocyanate are preferably hexamethylene diisocyanate.The preparation method of base polyurethane prepolymer for use as is using above-mentioned formula as raw material, by that will react to obtain intermediate with polyisocyanates and aliphatic or alicyclic diisocyanate again after the vacuum dehydration of polyether polyol elder generation.For the preparation method of the environmental protection polyureas sports ground surface layer by the way that the above-mentioned base polyurethane prepolymer for use as being prepared and curing agent to be obtained by mixing, the sports ground surface layer being prepared has good anti-yellowing property, is a kind of ep-type material.
Description
Technical field
The present invention relates to polyurethane material technical fields, and in particular to base polyurethane prepolymer for use as, preparation method and ring
Protect the preparation method of polyureas sports ground surface layer.
Background technique
It in general is by base polyurethane prepolymer for use as and the mixing cured film forming of curing agent, poly- ammonia when producing sports ground surface layer
Ester performed polymer is to react to obtain by polyisocyanates and polyether polyol, and curing agent is generally the pure and mild diamines chain extension of polyether polyols
Agent, and assist some fillers, auxiliary agent etc..Base polyurethane prepolymer for use as and curing agent are mixed in a certain proportion, while a small amount of urge is added
Agent and diluent and then film-forming.
The prior art is having the following problems in the feature of environmental protection: (1) when produce base polyurethane prepolymer for use as, the polyisocyanic acid of addition
Ester is mostly the toluene di-isocyanate(TDI) (TDI) of toxicity, and vapour pressure is big, volatile poison gas, is the main source of malicious runway；(2) solid
Diamines in agent component B mostly uses not card (MOCA), and although Mo Ka is had excellent performance, be carcinogenic substance, be easy to production exercise
Author brings harm；(3) volatile, toxic solvent, such as benzene, toluene are commonly incorporated into curing agent component B；(4) curing agent second
Poisonous and hazardous plasticizer, such as phthalate are commonly incorporated into component, boy's sterilization can be made by being excessively used；(5) first and second
When component mixes, the toxic heavy metal catalysts such as lead, mercury are usually added；(6) when the first and second components mix, the diluent of addition
It is mostly toxic ethyl acetate class solvent, smell is big, and irritation is big.
The prior art has the following problems in performance: (1) weatherability is poor；(2) resistance to soiling is poor, easily attracting dust, table
Face is dirty, should not clean；(3) adhesive property is poor, and basecoat material is easy to disconnect with surface material, separates.In addition, the prior art
There is also the problems that construction is inconvenient, the problems such as easily bubbling in the construction process, bring difficulty to construction.
Summary of the invention
The purpose of the present invention is to provide a kind of base polyurethane prepolymer for use as and preparation method thereof, it is intended to improve the color inhibition of product
Performance and environmental-protecting performance.
Another object of the present invention is to provide a kind of preparation method of environmentally friendly polyureas sports ground surface layer, anti-yellowing properties
It is good, it is suitable for promoting and applying.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The invention proposes a kind of base polyurethane prepolymer for use as, and according to parts by weight, preparing raw material includes polyether polyol 55-
90 parts, 10-25 parts of polyisocyanates and aliphatic or 2-6 parts of alicyclic diisocyanate；
Aliphatic or alicyclic diisocyanate are preferably hexamethylene diisocyanate.
The present invention also proposes a kind of preparation method of base polyurethane prepolymer for use as, comprising the following steps:
By polyether polyol under the conditions of 100-110 DEG C of temperature after vacuum dehydration 1-3h, then with polyisocyanates and
Aliphatic or alicyclic diisocyanate react 1-3h under the conditions of 75-85 DEG C of temperature and obtain intermediate；
Preferably, the raw material of base polyurethane prepolymer for use as further includes silane modifier and plasticizer, the preparation of base polyurethane prepolymer for use as
Method further includes mixing intermediate with silane modifier and reacting 1-3h under the conditions of 75-85 DEG C of temperature, then will reaction
Mixture afterwards reacts 15-50min under the conditions of being blended in 50-70 DEG C of temperature with plasticizer.
The present invention also proposes a kind of preparation method of environmentally friendly polyureas sports ground surface layer, comprising the following steps:
Base polyurethane prepolymer for use as is prepared according to above-mentioned preparation method；
Base polyurethane prepolymer for use as is uniformly mixed with curing agent；
Preferably, the mass ratio of base polyurethane prepolymer for use as and curing agent is 1:1-3.
The beneficial effect that the embodiment of the present invention provides a kind of base polyurethane prepolymer for use as is: it is by improving base polyurethane prepolymer for use as
Formula improves product yellowing resistance by the way that aliphatic or alicyclic diisocyanate is added and the adjustment of material rate is cooperated to reach
The purpose of energy, and cost is relatively low for preparation.
The embodiment of the invention also provides a kind of preparation methods of base polyurethane prepolymer for use as, using above-mentioned formula as raw material, lead to
Cross to react to obtain with polyisocyanates and aliphatic or alicyclic diisocyanate again after the vacuum dehydration of polyether polyol elder generation
Intermediate.Preparation that method is simple, obtained urethane intermediates can be used for preparing the good polyurethane of anti-yellowing property and produce
Product.
The embodiment of the present invention also proposes a kind of preparation method of environmentally friendly polyureas sports ground surface layer, by being prepared into above-mentioned
To base polyurethane prepolymer for use as and curing agent be obtained by mixing, the sports ground surface layer being prepared has good anti-yellowing property.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to base polyurethane prepolymer for use as provided in an embodiment of the present invention, preparation method and environmentally friendly polyureas sports ground surface layer
Preparation method be specifically described.
A kind of base polyurethane prepolymer for use as provided in an embodiment of the present invention, according to parts by weight, preparing raw material includes that polyethers is more
First alcohol 55-90 parts, 10-25 parts of polyisocyanates and aliphatic or 2-6 parts of alicyclic diisocyanate.
It should be noted that by the way that aliphatic or alicyclic diisocyanate is added and the adjustment of material rate is cooperated to reach
The purpose of product anti-yellowing property is improved, and due to being lower with the use of preparation cost with polyisocyanates.Inventors have found that
It is critically important to the dosage that reaches preferable anti-yellowing property aliphatic or alicyclic diisocyanate, if dosage is excessive or very few
It will lead to the decline of base polyurethane prepolymer for use as comprehensive performance, and the very few anti-yellowing property of dosage is poor, dosage excessive cost is higher.
The reason of addition aliphatic or alicyclic diisocyanate can be improved its anti-yellowing property can be in its molecular structure not
Contain phenyl ring.
Specifically, aliphatic or alicyclic diisocyanate can be hexamethylene diisocyanate (HDI), 4,4'- bis-
Diphenylmethane diisocyanate (HMDI) and isophorone diisocyanate (IPDI), preferably hexa-methylene diisocyanate
Ester.Hexamethylene diisocyanate is used to be more advantageous to the anti-yellowing property for promoting polyurethane products for raw material.
Preferably, the degree of functionality of polyether polyol is 2-3, molecular weight 1000-5000；It is highly preferred that polyether polyol
Including 35-50 parts of the first polyether polyol, 15-25 parts of the second polyether polyol and 5-15 parts of third polyether polyol；Wherein,
The degree of functionality of one polyether polyol is 3, molecular weight 4500-5500；The degree of functionality of second polyether polyol is 2, and molecular weight is
3500-4500；The degree of functionality of third polyether polyol is 2, molecular weight 800-1200.It is further preferred that polyether polyol
Including 43-48 parts of the first polyether polyol, 18-22 parts of the second polyether polyol and 6-10 parts of third polyether polyol.
You need to add is that inventor advanced optimizes the formula of base polyurethane prepolymer for use as, use three of the above polyalcohol for
The anti-yellowing property for the product that raw material is prepared is best, and comprehensive performance is also very excellent.First polyether polyol, second gather
Ethoxylated polyhydric alcohol and third polyether polyol are purchased from Shanghai Jia Hua Chemical Co., Ltd. or Shandong blue star Dong great Chemical Co., Ltd.,
For existing raw material.
Specifically, polyisocyanates is selected from Toluene-2,4-diisocyanate, 4- diisocyanate (TDI), bis- isocyanide of diphenyl methane -4,4'-
Acid esters (MDI) and 3- isocyanates methylene -3,5, any one in 5- trimethylcyclohexylisocyanate (IPDI)；It is excellent
It is selected as diphenyl methane -4,4'- diisocyanate.Using MDI for raw material, on the one hand its vapour pressure is small, toxicity is low；On the other hand
MDI and aliphatic or alicyclic diisocyanate cooperation anti-yellowing property are very excellent.
Preferably, the raw material of base polyurethane prepolymer for use as further includes 1-4 parts of silane modifier, preferably 1.5-2.5 parts；It is preferred that
Ground, silane modifier is polysiloxane compound, and the molecular weight of silane modifier is 300-1500.Inventor has found using poly-
Silicone compounds can significantly improve the hydrophobicity of product as silane modifier, make product have easy cleaning, bear dirty etc. it is excellent
Point.
Preferably, the raw material of base polyurethane prepolymer for use as further includes 2-10 parts of plasticizer, preferably 5-9 parts；Wherein, plasticizer selects
From one of methyl hexadecanoate or soybean grease or a variety of.Plasticizer is selectively added according to the viscosity of raw material, and dosage is unsuitable
Excessively.
The embodiment of the invention also provides a kind of preparation methods of base polyurethane prepolymer for use as, comprising the following steps:
By polyether polyol under the conditions of 100-110 DEG C of temperature after vacuum dehydration 1-3h, then with polyisocyanates and
Aliphatic or alicyclic diisocyanate react 1-3h under the conditions of 75-85 DEG C of temperature and obtain intermediate.Inventor passes through tune
The temperature and time of reaction process is controlled further to promote the anti-yellowing property of base polyurethane prepolymer for use as, and then is promoted finally obtained
The anti-yellowing property of polyurethane products.
In some embodiments, the raw material of base polyurethane prepolymer for use as further includes silane modifier and plasticizer, polyurethane prepolymer
The preparation method of body further includes mixing intermediate with silane modifier and reacting 1-3h under the conditions of 75-85 DEG C of temperature, so
The mixture after reaction is blended under the conditions of 50-70 DEG C of temperature with plasticizer afterwards and reacts 15-50min.Silane is added by several times
Modifying agent and plasticizer simultaneously control reaction temperature and time so that the anti-yellowing property of finally obtained base polyurethane prepolymer for use as is excellent
It is good, and have good hydrophobic performance.
The embodiment of the invention also provides a kind of preparation methods of environmentally friendly polyureas sports ground surface layer, comprising the following steps: root
Base polyurethane prepolymer for use as is prepared according to above-mentioned preparation method, base polyurethane prepolymer for use as is uniformly mixed with curing agent；Preferably, polyurethane is pre-
The mass ratio of aggressiveness and curing agent is 1:1-3.Base polyurethane prepolymer for use as and curing agent are uniformly mixed and are laid in process of deployment
At required thickness.The advantages that sports ground surface layer has good anti-yellowing property, is also equipped with easy cleaning, bears dirty.
You need to add is that curing agent can use commercial products, curing agent and the embodiment of the present invention are prepared
Base polyurethane prepolymer for use as is uniformly mixed obtained sports ground surface material and just has good anti-yellowing property.
Preferably, according to the mass fraction, curing agent includes 1-5 parts of diamine curing agent, 10-25 parts of polyetheramine and plasticizer
15-30 parts, wherein the molecular weight of polyetheramine is 1500-2500.Use diamines chemicals for curing agent, and cooperate polyetheramine and
Plasticizer makes sports ground surface material avoid the occurrence of bubbling problem.This may be due in curing agent do not contain polyether polyol,
But aminated compounds is used, and the relationship of reaction rate is substantially when " active hydrogen " is reacted with NCO are as follows: amine > primary alconol > water >
Secondary alcohol, it is seen that the introducing of amine can block NCO to react with water, and preferential generation amine is reacted with NCO's, generate polyureas.In this way, using
Curing agent provided in an embodiment of the present invention thoroughly solves the problems, such as that construction is bubbled, while the adhesive property of polyureas is much larger than poly- ammonia
Ester, can be Nian Jie with primary coat good, improves bonding problem.
Inventor is further optimized the formula of curing agent, to promote the anti-yellowing property of product, and avoids applying
Work is bubbled problem.It is highly preferred that curing agent includes 1-3 parts of diamine curing agent, 12-18 parts of polyetheramine and 23-28 parts of plasticizer.
It should be pointed out that the embodiment of the present invention uses aminated compounds for curing agent, the use not blocked is avoided, the solidification
Agent not only performance with do not block equally excellent, but also reaction rate is fast, can effectively improve curing rate, so as to avoid a huge sum of money
The use of metal catalyst, greatly improves the feature of environmental protection.
Specifically, diamine curing agent is commercially available diamine compounds (primary amine or secondary amine of the molecular weight less than 500), is purchased from
Ten thousand China 6200, unilink4200, unilink4100, E100, the excellent profit FPR06 in Guangzhou etc..Polyetheramine is also commercial products, preferably
For D2000.Plasticizer is or mixtures thereof methyl hexadecanoate or one kind of soybean grease.
Further preferably, curing agent further includes 0.1-1 parts of dispersing agent, 1-10 parts of pigment, 40-65 parts of filler and auxiliary agent 0.5-
1.5 part；Preferably, curing agent further includes 0.3-0.7 parts of dispersing agent, 2-5 parts of pigment, 50-55 parts of filler and auxiliary agent 0.3-1.7
Part.Using the methyl hexadecanoate of environment-friendly type as plasticizer, while the dispersing agent of environment-friendly type is added, improves the uniform of component B
Property, viscosity is reduced, the use of diluent has been evaded, is really accomplished environmentally protective.
Specifically, auxiliary agent includes 0.1-0.7 parts and age resister 0.2-1 parts of thickener.Pigment be selected from titanium dioxide, iron oxide red and
Any one in iron oxide yellow；Any one or more of filler in clay, talcum powder, coarse whiting, light calcium and nanometer calcium；Thickening
Any one or more of agent in clay, polyacrylic acid and fumed silica.In specific preparation process, Ke Yigen
According to needing to select suitable pigment, filler and thickener.
Specifically, thickener can be fumed silica, and dispersing agent is non-ionic surfactant substance, excellent
Select the FT-201 of Fitow brother company.Age resister includes the combination of ultraviolet absorber and antioxidant, and specific product is not wanted
It asks.
The preparation method of curing agent is the following steps are included: equal by diamine curing agent, polyetheramine, plasticizer and dispersant
It is even to be used as liquid material；Pigment, filler and auxiliary agent are uniformly mixed and are used as powder；Powder is added in general liquid material after mixing
Uniform fineness is ground on grinder；Material after grinding is mixed with remaining liquid material to obtain the final product.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment provides a kind of base polyurethane prepolymer for use as, and according to parts by weight, preparing raw material includes polyether polyol 55
Part, 10 parts of polyisocyanates and 2 parts of hexamethylene diisocyanate；Wherein, the degree of functionality of polyether polyol be 2, molecular weight about
It is 1000, polyisocyanates is diphenyl methane -4,4'- diisocyanate.
The present embodiment also provides a kind of preparation method of base polyurethane prepolymer for use as, using above-mentioned formula as raw material, comprising: by polyethers
Polyalcohol is then different with polyisocyanates and diphenyl methane -4,4'- bis- under the conditions of 100 DEG C of temperature after vacuum dehydration 1h
Cyanate reacts 3h under the conditions of 75 DEG C of temperature and obtains intermediate.
Embodiment 2
The present embodiment provides a kind of base polyurethane prepolymer for use as, and according to parts by weight, preparing raw material includes polyether polyol 90
Part, 25 parts of polyisocyanates and 6 parts of hexamethylene diisocyanate；Wherein, the degree of functionality of polyether polyol be 3, molecular weight about
It is 5000, polyisocyanates is diphenyl methane -4,4'- diisocyanate.
The present embodiment also provides a kind of preparation method of base polyurethane prepolymer for use as, using above-mentioned formula as raw material, comprising: by polyethers
Polyalcohol is then different with polyisocyanates and diphenyl methane -4,4'- bis- under the conditions of 110 DEG C of temperature after vacuum dehydration 3h
Cyanate reacts 1h under the conditions of 85 DEG C of temperature and obtains intermediate.
Embodiment 3
The present embodiment provides a kind of base polyurethane prepolymer for use as, and according to parts by weight, preparing raw material includes polyether polyol 55
Part, 25 parts of polyisocyanates, 6 parts of hexamethylene diisocyanate, 1 part of silane modifier and 2 parts of methyl hexadecanoate plasticizer；Its
In, polyether polyol includes 35 parts of the first polyether polyol, 15 parts of the second polyether polyol and 5 parts of third polyether polyol, the
The degree of functionality of one polyether polyol is 3, and molecular weight is about 4500；The degree of functionality of second polyether polyol is 2, and molecular weight is about
3500；The degree of functionality of third polyether polyol is 2, and molecular weight is about 800.Polyisocyanates is that diphenyl methane -4,4'- two is different
Cyanate, silane modifier is polysiloxane compound, and the molecular weight of silane modifier is about 300.
The present embodiment also provides a kind of preparation method of base polyurethane prepolymer for use as, using above-mentioned formula as raw material, comprising: by polyethers
Polyalcohol is then different with polyisocyanates and diphenyl methane -4,4'- bis- under the conditions of 110 DEG C of temperature after vacuum dehydration 3h
Cyanate reacts 1h under the conditions of 80 DEG C of temperature and obtains intermediate.
Intermediate is mixed with silane modifier and reacts 3h under the conditions of 75 DEG C of temperature, then by the mixing after reaction
Object reacts 50min under the conditions of being blended in 50 DEG C of temperature with plasticizer.
Embodiment 4
The present embodiment provides a kind of base polyurethane prepolymer for use as, and according to parts by weight, preparing raw material includes polyether polyol 90
Part, 25 parts of polyisocyanates, 6 parts of hexamethylene diisocyanate, 4 parts of silane modifier and 10 parts of methyl hexadecanoate plasticizer；
Wherein, polyether polyol includes 50 parts of the first polyether polyol, 25 parts of the second polyether polyol and 15 parts of third polyether polyol,
The degree of functionality of first polyether polyol is 3, and molecular weight is about 5500；The degree of functionality of second polyether polyol is 2, and molecular weight is about
4500；The degree of functionality of third polyether polyol is 2, and molecular weight is about 1200.Polyisocyanates is diphenyl methane -4,4'- two
Isocyanates, silane modifier is polysiloxane compound, and the molecular weight of silane modifier is about 1500.
The present embodiment also provides a kind of preparation method of base polyurethane prepolymer for use as, using above-mentioned formula as raw material, comprising: by polyethers
Polyalcohol is then different with polyisocyanates and diphenyl methane -4,4'- bis- under the conditions of 110 DEG C of temperature after vacuum dehydration 2h
Cyanate reacts 2h under the conditions of 80 DEG C of temperature and obtains intermediate.
Intermediate is mixed with silane modifier and reacts 1h under the conditions of 85 DEG C of temperature, then by the mixing after reaction
Object reacts 15min under the conditions of being blended in 70 DEG C of temperature with plasticizer.
Embodiment 5
The present embodiment provides a kind of base polyurethane prepolymer for use as, and according to parts by weight, preparing raw material includes polyether polyol 67
Part, 20 parts of polyisocyanates, 4 parts of hexamethylene diisocyanate, 1.5 parts of silane modifier and 5 parts of methyl hexadecanoate plasticizer；
Wherein, polyether polyol includes 43 parts of the first polyether polyol, 18 parts of the second polyether polyol and 6 parts of third polyether polyol,
The degree of functionality of first polyether polyol is 3, and molecular weight is about 5000；The degree of functionality of second polyether polyol is 2, and molecular weight is about
4000；The degree of functionality of third polyether polyol is 2, and molecular weight is about 1000.Polyisocyanates is diphenyl methane -4,4'- two
Isocyanates, silane modifier is polysiloxane compound, and the molecular weight of silane modifier is about 800.
The present embodiment also provides a kind of preparation method of base polyurethane prepolymer for use as, using above-mentioned formula as raw material, comprising: by polyethers
Polyalcohol is then different with polyisocyanates and diphenyl methane -4,4'- bis- under the conditions of 110 DEG C of temperature after vacuum dehydration 2h
Cyanate reacts 2h under the conditions of 80 DEG C of temperature and obtains intermediate.
Intermediate is mixed with silane modifier and reacts 2h under the conditions of 80 DEG C of temperature, then by the mixing after reaction
Object reacts 30min under the conditions of being blended in 60 DEG C of temperature with plasticizer.
Embodiment 6
The present embodiment provides a kind of base polyurethane prepolymer for use as, and according to parts by weight, preparing raw material includes polyether polyol 80
Part, 20 parts of polyisocyanates, 4 parts of hexamethylene diisocyanate, 2.5 parts of silane modifier and 9 parts of soybean grease plasticizer；Its
In, polyether polyol includes 48 parts of the first polyether polyol, 22 parts of the second polyether polyol and 10 parts of third polyether polyol, the
The degree of functionality of one polyether polyol is 3, and molecular weight is about 5000；The degree of functionality of second polyether polyol is 2, and molecular weight is about
4000；The degree of functionality of third polyether polyol is 2, and molecular weight is about 1000.Polyisocyanates is diphenyl methane -4,4'- two
Isocyanates, silane modifier is polysiloxane compound, and the molecular weight of silane modifier is about 800.
The present embodiment also provides a kind of preparation method of base polyurethane prepolymer for use as, using above-mentioned formula as raw material, specific steps ginseng
According to embodiment 5.
Embodiment 7
The present embodiment provides a kind of base polyurethane prepolymer for use as, according to parts by weight, prepare raw material and the substantially phase of embodiment 6
Together, it the difference is that only that polyisocyanates is Toluene-2,4-diisocyanate, 4- diisocyanate (TDI).
The present embodiment also provides a kind of preparation method of base polyurethane prepolymer for use as, using above-mentioned formula as raw material, specific steps ginseng
According to embodiment 5.
Embodiment 8
The present embodiment provides a kind of base polyurethane prepolymer for use as, according to parts by weight, prepare raw material and the substantially phase of embodiment 6
Together, it the difference is that only that polyisocyanates is 3- isocyanates methylene -3,5,5- trimethylcyclohexylisocyanate
(IPDI)。
The present embodiment also provides a kind of preparation method of base polyurethane prepolymer for use as, using above-mentioned formula as raw material, specific steps ginseng
According to embodiment 5.
Embodiment 9
The present embodiment provides a kind of base polyurethane prepolymer for use as, according to parts by weight, prepare raw material and the substantially phase of embodiment 6
Together, it the difference is that only that hexamethylene diisocyanate replaces with 4,4'- dicyclohexyl methyl hydride diisocyanate (HMDI).
The present embodiment also provides a kind of preparation method of base polyurethane prepolymer for use as, using above-mentioned formula as raw material, specific steps ginseng
According to embodiment 5.
Embodiment 10
The present embodiment provides a kind of preparation methods of environmentally friendly polyureas sports ground surface layer, comprising the following steps:
Base polyurethane prepolymer for use as is prepared according to the method for embodiment 1.
10 parts of polyetheramine, 15 parts of methyl hexadecanoate plasticizer and the propylene for being about 1500 by 1 part of diamine compound, molecular weight
0.1 part of acid esters high-molecular type dispersing agent be uniformly mixed obtain liquid material；By 1 part of titanium dioxide, 40 parts of talcum powder and 0.5 part of clay mixing
Uniformly obtain powder；It is uniformly mixed to obtain with remaining liquid material again after powder is mixed evenly and is ground with the liquid material of half
Curing agent product.
Above-mentioned base polyurethane prepolymer for use as and curing agent product are uniformly mixed with the ratio of 1:1.
Embodiment 11
The present embodiment provides a kind of preparation methods of environmentally friendly polyureas sports ground surface layer, comprising the following steps:
Base polyurethane prepolymer for use as is prepared according to the method for embodiment 4.
25 parts of polyetheramine, 30 parts of methyl hexadecanoate plasticizer and the propylene for being about 2500 by 5 parts of diamine compound, molecular weight
1 part of acid esters high-molecular type dispersing agent be uniformly mixed obtain liquid material；By 10 parts of titanium dioxide, 65 parts of talcum powder and 1.5 parts of clay mixing
Uniformly obtain powder；It is uniformly mixed to obtain with remaining liquid material again after powder is mixed evenly and is ground with the liquid material of half
Curing agent product.
Above-mentioned base polyurethane prepolymer for use as and curing agent product are uniformly mixed with the ratio of 1:3.
Embodiment 12
The present embodiment provides a kind of preparation methods of environmentally friendly polyureas sports ground surface layer, comprising the following steps:
Base polyurethane prepolymer for use as is prepared according to the method for embodiment 5.
12 parts of polyetheramine, 23 parts of methyl hexadecanoate plasticizer and the propylene for being about 2000 by 1 part of diamine compound, molecular weight
0.3 part of acid esters high-molecular type dispersing agent be uniformly mixed obtain liquid material；2 parts of iron oxide yellow, 50 parts of coarse whiting and 0.3 part of clay are uniformly mixed
Obtain powder；It is uniformly mixed and is solidified with remaining liquid material again after powder is mixed evenly and is ground with the liquid material of half
Agent product.
Above-mentioned base polyurethane prepolymer for use as and curing agent product are uniformly mixed with the ratio of 1:2.
Embodiment 13
The present embodiment provides a kind of preparation methods of environmentally friendly polyureas sports ground surface layer, comprising the following steps:
Base polyurethane prepolymer for use as is prepared according to the method for embodiment 6.
18 parts of polyetheramine, 28 parts of methyl hexadecanoate plasticizer and the propylene for being about 2000 by 3 parts of diamine compound, molecular weight
0.7 part of acid esters high-molecular type dispersing agent be uniformly mixed obtain liquid material；By 5 parts of iron oxide red, 55 parts of light calcium and 1.7 parts of fumed silica
It is uniformly mixed and obtains powder；It is uniformly mixed again with remaining liquid material after powder is mixed evenly and is ground with the liquid material of half
Obtain curing agent product.
Above-mentioned base polyurethane prepolymer for use as and curing agent product are uniformly mixed with the ratio of 1:2.
Embodiment 14
The present embodiment provides a kind of preparation methods of environmentally friendly polyureas sports ground surface layer, and specific steps and embodiment 13 are substantially
It is identical, the difference is that: base polyurethane prepolymer for use as is prepared according to the method for embodiment 7.
Embodiment 15
The present embodiment provides a kind of preparation methods of environmentally friendly polyureas sports ground surface layer, and specific steps and embodiment 13 are substantially
It is identical, the difference is that: base polyurethane prepolymer for use as is prepared according to the method for embodiment 8.
Embodiment 16
The present embodiment provides a kind of preparation methods of environmentally friendly polyureas sports ground surface layer, and specific steps and embodiment 13 are substantially
It is identical, the difference is that: base polyurethane prepolymer for use as is prepared according to the method for embodiment 9.
Comparative example 1
The present embodiment provides a kind of preparation methods of environmentally friendly polyureas sports ground surface layer, and specific steps and embodiment 13 are substantially
It is identical, the difference is that: it does not include diamine compound in the formula of curing agent product, and 21 parts of polyetheramine.
Comparative example 2
The present embodiment provides a kind of preparation methods of environmentally friendly polyureas sports ground surface layer, and specific steps and embodiment 13 are substantially
It is identical, the difference is that: curing agent uses commercial products, is used as curing agent using not card.
Comparative example 3
This comparative example provides a kind of base polyurethane prepolymer for use as, according to parts by weight, prepares raw material and the substantially phase of embodiment 6
Together, the difference is that: hexamethylene diisocyanate dosage be 8 parts (increasing its dosage).
This comparative example also provides a kind of preparation method of base polyurethane prepolymer for use as, using above-mentioned formula as raw material, specific steps ginseng
According to embodiment 5.
This comparative example also provides a kind of preparation method of environmentally friendly polyureas sports ground surface layer, and specific steps and embodiment 13 are big
Cause it is identical, the difference is that: base polyurethane prepolymer for use as is prepared using the method for this comparative example.
Comparative example 4
This comparative example provides a kind of base polyurethane prepolymer for use as, according to parts by weight, prepares raw material and the substantially phase of embodiment 6
Together, the difference is that: hexamethylene diisocyanate dosage be 1 part (reducing its dosage), polyisocyanates be 23 part (two
The total dosage of person keeps identical).
This comparative example also provides a kind of preparation method of base polyurethane prepolymer for use as, using above-mentioned formula as raw material, specific steps ginseng
According to embodiment 5.
This comparative example also provides a kind of preparation method of environmentally friendly polyureas sports ground surface layer, and specific steps and embodiment 13 are big
Cause it is identical, the difference is that: base polyurethane prepolymer for use as is prepared using the method for this comparative example.
Comparative example 5
This comparative example provides a kind of base polyurethane prepolymer for use as, according to parts by weight, prepares raw material and the substantially phase of embodiment 6
Together, the difference is that: be added without hexamethylene diisocyanate, the dosage of polyisocyanates is 24 parts.
This comparative example also provides a kind of preparation method of base polyurethane prepolymer for use as, using above-mentioned formula as raw material, specific steps ginseng
According to embodiment 5.
This comparative example also provides a kind of preparation method of environmentally friendly polyureas sports ground surface layer, and specific steps and embodiment 13 are big
Cause it is identical, the difference is that: base polyurethane prepolymer for use as is prepared using the method for this comparative example.
Test example 1
Using the xanthochromia series in conventional method testing example 10-16 and comparative example 1-4, in polyurethane industries among others,
Xanthochromia series Δ Yi is divided according to yellowness index:
0 grade: without discoloration, Δ Yi≤1.5；
1 grade: very light discolouration, 1.6 < Δ Yi≤3.0；
2 grades: light discolouration, 3.1 < Δ Yi≤6.0；
3 grades: obvious discoloration, 6.1 < Δ Yi≤9.0；
4 grades: larger discoloration, 9.1 < Δ Yi≤12.0；
5 grades: serious discoloration, 12.0 < Δ Yi.
Test result is shown: (1) after carrying out accelerated ageing 500 hours at identical conditions using ultraviolet ageing, being implemented
Example 10-16 in material xanthochromia series successively are as follows: 2 grades, 2 grades, 1 grade, 1 grade, 2 grades, 2 grades and 2 grades；The xanthochromia grade of comparative example 1-5
Number is successively are as follows: 2 grades, 2 grades, 1 grade, 3 grades and 4 grades.
From test result it is found that the poly- ammonia being prepared using the base polyurethane prepolymer for use as formula provided in the embodiment of the present invention
Material after ester performed polymer and curing agent curing molding has good anti-yellowing property.
Comparative example 13, comparative example 1 and comparative example 2 have not after using commercially available curing agent curing molding
Wrong anti-yellowing property, and more preferably using anti-yellowing property after hardener formula curing molding provided in an embodiment of the present invention.
Comparative example 13 and comparative example 3-5 are it is found that the addition of aliphatic isocyanates influences very anti-yellowing property
Significantly, used in amounts will control in a certain range, and dosage is excessive can not to reach better color inhibition effect, and dosage is very few resistance to
Xanthochromia effect is undesirable.
Comparative example 13-16 using hexamethylene diisocyanate as aliphatic isocyanates it is found that be added, and adopt
Color inhibition effect is best when with diphenyl methane -4,4'- diisocyanate being polyisocyanates.
Test example 2
All-round property testing is carried out to the material in embodiment 13 using DB65/T 3918-2016 standard, test result is shown in
Table 1.
1 sports ground surface layer performance test results of table
As shown in Table 1, the material that the preparation method of environmentally friendly polyureas sports ground surface layer provided in an embodiment of the present invention is prepared
The high comprehensive performance of material does not contain poisonous and hazardous substance, is a kind of ep-type material, is suitable for promoting and applying.
In conclusion a kind of base polyurethane prepolymer for use as provided by the invention and preparation method thereof, pre- by improving polyurethane
The formula of aggressiveness, it is resistance to by the way that aliphatic or alicyclic diisocyanate is added and the adjustment of material rate is cooperated to reach raising product
The purpose of xanthochromia performance, and cost is relatively low for preparation.
The embodiment of the present invention also proposes a kind of preparation method of environmentally friendly polyureas sports ground surface layer, by being prepared into above-mentioned
To base polyurethane prepolymer for use as and curing agent be obtained by mixing, the sports ground surface layer being prepared has good anti-yellowing property, is
A kind of material of environment-friendly type.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of base polyurethane prepolymer for use as, which is characterized in that according to parts by weight, preparing raw material includes polyether polyol 55-90
Part, 10-25 parts of polyisocyanates and aliphatic or 2-6 parts of alicyclic diisocyanate；
The aliphatic or alicyclic diisocyanate are preferably hexamethylene diisocyanate.
2. base polyurethane prepolymer for use as according to claim 1, which is characterized in that the degree of functionality of the polyether polyol is 2-3,
Molecular weight is 1000-5000；
Preferably, the polyether polyol includes 35-50 parts of the first polyether polyol, 15-25 parts of the second polyether polyol and the
Three 5-15 parts of polyether polyol；Wherein, the degree of functionality of first polyether polyol is 3, molecular weight 4500-5500；It is described
The degree of functionality of second polyether polyol is 2, molecular weight 3500-4500；The degree of functionality of the third polyether polyol is 2, point
Son amount is 800-1200；
It is highly preferred that the polyether polyol include 43-48 parts of the first polyether polyol, 18-22 parts of the second polyether polyol and
6-10 parts of third polyether polyol.
3. base polyurethane prepolymer for use as according to claim 1, which is characterized in that the polyisocyanates is selected from Toluene-2,4-diisocyanate, 4-
Diisocyanate, diphenyl methane -4,4'- diisocyanate and 3- isocyanates methylene -3,5,5- trimethylcyclohexyl
Any one in isocyanates；
Preferably diphenyl methane -4,4'- diisocyanate.
4. base polyurethane prepolymer for use as according to claim 1, which is characterized in that the raw material of the base polyurethane prepolymer for use as further includes
1-4 parts of silane modifier, preferably 1.5-2.5 parts；
Preferably, the silane modifier is polysiloxane compound, and the molecular weight of the silane modifier is 300-1500.
5. base polyurethane prepolymer for use as according to claim 1, which is characterized in that the raw material of the base polyurethane prepolymer for use as further includes
2-10 parts of plasticizer, preferably 5-9 parts；
Wherein, the plasticizer is selected from one of methyl hexadecanoate or soybean grease or a variety of.
6. the preparation method of base polyurethane prepolymer for use as described in any one of -5 according to claim 1, which is characterized in that including following step
It is rapid:
By the polyether polyol under the conditions of 100-110 DEG C of temperature after vacuum dehydration 1-3h, then with the polyisocyanates,
And the aliphatic or alicyclic diisocyanate react 1-3h under the conditions of 75-85 DEG C of temperature and obtain intermediate；
Preferably, the raw material of the base polyurethane prepolymer for use as further includes silane modifier and plasticizer, the base polyurethane prepolymer for use as
Preparation method further includes mixing the intermediate with silane modifier and reacting 1-3h under the conditions of 75-85 DEG C of temperature, so
The mixture after reaction is blended under the conditions of 50-70 DEG C of temperature with plasticizer afterwards and reacts 15-50min.
7. a kind of preparation method of environmental protection polyureas sports ground surface layer, which comprises the following steps:
Preparation method according to claim 6 prepares the base polyurethane prepolymer for use as；
The base polyurethane prepolymer for use as is uniformly mixed with curing agent；
Preferably, the mass ratio of the base polyurethane prepolymer for use as and the curing agent is 1:1-3.
8. the preparation method of environmental protection polyureas sports ground surface layer according to claim 7, which is characterized in that press mass fraction
Meter, the curing agent include 1-5 parts of diamine curing agent, 10-25 parts of polyetheramine and 15-30 parts of plasticizer, wherein the polyetheramine
Molecular weight be 1500-2500；
Preferably, the curing agent includes 1-3 parts of diamine curing agent, 12-18 parts of polyetheramine and 23-28 parts of plasticizer.
9. the preparation method of environmental protection polyureas sports ground surface layer according to claim 7, which is characterized in that the curing agent is also
Including 0.1-1 parts of dispersing agent, 1-10 parts of pigment, 40-65 parts of filler and 0.5-1.5 parts of auxiliary agent；
Preferably, the curing agent further includes 0.3-0.7 parts of dispersing agent, 2-5 parts of pigment, 50-55 parts of filler and auxiliary agent 0.3-1.7
Part；
It is highly preferred that the auxiliary agent includes 0.1-0.7 parts and age resister 0.2-1 parts of thickener.
10. the preparation method of environmental protection polyureas sports ground surface layer according to claim 9, which is characterized in that the pigment choosing
From any one in titanium dioxide, iron oxide red and iron oxide yellow；The filler is in clay, talcum powder, coarse whiting, light calcium and nanometer calcium
Any one or more；Any one or more of the thickener in clay, polyacrylic acid and fumed silica.
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Cited By (2)
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| CN111454563A (en) * | 2020-04-29 | 2020-07-28 | 一起划冰雪体育发展(福建)有限公司 | Normal-temperature ice and preparation method thereof |
| CN114106682A (en) * | 2021-11-08 | 2022-03-01 | 广东高捷体育产业有限公司 | Playground floor coating material and preparation method and application thereof |
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| US20020156168A1 (en) * | 1997-06-04 | 2002-10-24 | Martin Schafer | Method for producing one-component sealing and coating compounds with a polyurethane base |
| CN1392171A (en) * | 2002-07-12 | 2003-01-22 | 丛树枫 | Preparation and use of elastic high-strength polyurthane prepolymer |
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Cited By (2)
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| CN111454563A (en) * | 2020-04-29 | 2020-07-28 | 一起划冰雪体育发展(福建)有限公司 | Normal-temperature ice and preparation method thereof |
| CN114106682A (en) * | 2021-11-08 | 2022-03-01 | 广东高捷体育产业有限公司 | Playground floor coating material and preparation method and application thereof |
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| CN109535385B (en) | 2020-01-17 |
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