CN113278130B - Modified HDI trimer, single-component polyurethane adhesive, preparation method of single-component polyurethane adhesive and pavement material - Google Patents
Modified HDI trimer, single-component polyurethane adhesive, preparation method of single-component polyurethane adhesive and pavement material Download PDFInfo
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- CN113278130B CN113278130B CN202110543440.1A CN202110543440A CN113278130B CN 113278130 B CN113278130 B CN 113278130B CN 202110543440 A CN202110543440 A CN 202110543440A CN 113278130 B CN113278130 B CN 113278130B
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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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/7887—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having two nitrogen atoms in the ring
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
Abstract
The invention discloses a modified HDI tripolymer, a single-component polyurethane adhesive, a preparation method of the single-component polyurethane adhesive and a pavement material. The structural formula of the modified HDI tripolymer is shown in the specification
Description
Technical Field
The invention relates to the field of modified isocyanate and polyurethane adhesive, and also relates to a pavement material.
Background
The polyurethane type sports track has the advantages of moderate hardness, good elasticity, good skid resistance, wear resistance and the like, is popular with the public, wherein the single-component moisture-curing polyurethane road surface layer glue is convenient to construct and excellent in performance, and can be directly dried in the open air after being laid. Most of the prior adhesives for polyurethane runways are synthesized by aromatic isocyanate (such as MDI and the like), while the yellowing resistance of aromatic isocyanate synthetic materials is poor, and particularly in the runways with high requirements on color, brightness and appearance performance, the aromatic polyurethane materials can change color and yellow after being used for a long time, thereby greatly influencing the aesthetic effect. In order to solve the problem of the existing aromatic polyurethane track material, one scheme is that a layer of single-component moisture-cured aliphatic polyurethane material is laid on a track surface layer, so that the discoloration problem of the aromatic polyurethane can be effectively improved, but the aliphatic isocyanate has disadvantages in the aspects of reaction activity, mechanical property and the like compared with aromatic isocyanate (such as MDI). Patent CN106700888A relates to a runway spraying surface layer material, which is synthesized by MDI and has poor weather resistance; patent CN103819647A relates to a moisture-curable single-component polyurethane material, which can be synthesized by Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Xylylene Diisocyanate (XDI) and dicyclohexylmethane diisocyanate (HMDI) in combination with amino-terminated polyether and latent curing agent, and the latent curing agent releases amine substances when meeting water, thus being not good for health; patent CN107892870A has used HDI biuret, HDI monomer mixture to synthesize a plastic course for surface course polyurethane mask layer, the product is two ingredient products, the construction step is numerous and remaining volatile monomer is more, the product security is lower.
In order to overcome the defects that the surface of the existing single-component aliphatic adhesive is slow in drying (dust-free time), long in curing time, needs to be improved in mechanical strength and the like, the single-component polyurethane adhesive which is short in drying time in outdoor exposure days, good in weather resistance and excellent in performance is very necessary to be developed.
Disclosure of Invention
The invention aims to provide a modified HDI trimer which is used for preparing a single-component polyurethane adhesive and used for a pavement paving material. Compared with the traditional aliphatic diisocyanate and polyether polyol system, the open-air curing speed of the polyurethane adhesive is high after construction, the weather resistance and the mechanical property of the adhesive are excellent after drying, and the problem that the existing aliphatic single-component moisture curing adhesive for the pavement is slow in drying speed is solved.
In order to solve the technical problems, the invention provides the following technical scheme:
a modified HDI trimer (modified hexamethylene diisocyanate trimer) having the formula:
a method of preparing a modified HDI trimer according to the invention comprises the steps of:
(1) oleic acid base hydroxyethyl imidazoline
Mixing hydrogen peroxide and formic acid, and reacting at 45-50 deg.C for 1.5-2h to obtain modified hydroxyethyl imidazoline
(2) Under the protection of nitrogen, HDI tripolymer and modified hydroxyethyl imidazoline react for 1-2 hours at 70-80 ℃, and NCO is measured to reach a theoretical value, so that the modified HDI tripolymer is obtained.
In a preferable embodiment, in step (1) of the present invention, after the reaction is completed, the reaction mixture is cooled to room temperature, and then is washed with water and distilled to dehydrate to obtain modified hydroxyethyl imidazoline.
In the step (1), the mass ratio of oleic acid hydroxyethyl imidazoline to hydrogen peroxide to formic acid is 50: 12-10: 0.5-0.8.
In the step (2), the molar ratio of the HDI trimer to the modified hydroxyethyl imidazoline is 1: 1-1.3, preferably 1: 1.1-1.2.
The equation for preparing the modified HDI trimer is shown below:
the modified HDI trimer is used for preparing yellowing-resistant single-component polyurethane adhesive for pavement materials.
The yellowing-resistant single-component polyurethane adhesive for the pavement paving material comprises the following components: based on 100 parts of the total mass part,
as a preferable scheme, the yellowing-resistant single-component polyurethane adhesive for the pavement paving material comprises the following components: based on 100 parts of the total mass part,
the aliphatic diisocyanate monomer is selected from one or more of dicyclohexyl methane diisocyanate (HMDI), isophorone diisocyanate (IPDI), cyclohexyl dimethylene diisocyanate (HXDI) and Hexamethylene Diisocyanate (HDI), and isophorone diisocyanate (IPDI) is preferred.
The polyether glycol is polypropylene oxide ether glycol with the number average molecular weight of 1500-4000, preferably 1800-2200.
The chain extender is one of ethylene glycol, 2-methyl-1, 3-propylene glycol, 1, 4-butanediol and diethylene glycol, and 1, 4-butanediol is preferred.
The cross-linking agent is trimethylolpropane.
The catalyst is one or more of dibutyltin dilaurate, tin isooctanoate and bismuth isooctanoate, preferably dibutyltin dilaurate.
The plasticizer is epoxy fatty acid methyl ester.
A preparation method of a single-component polyurethane adhesive for a pavement paving material comprises the following steps: adding polyether polyol, a chain extender, a cross-linking agent and a catalyst into a reaction kettle, heating to 70-80 ℃, adding an aliphatic diisocyanate monomer and a modified HDI trimer, reacting for 2-3h, measuring the NCO value to reach a theoretical value, adding a plasticizer, and continuously stirring for 0.5-1h to obtain the single-component polyurethane adhesive.
The aliphatic isocyanate trimer modifier is introduced into the single-component polyurethane adhesive, and the beneficial effects are that an imidazoline structure with a tertiary amine group and an epoxy group is introduced into the HDI trimer, the self-catalysis effect of the structure promotes the reaction speed of the single-component polyurethane adhesive with moisture after construction, the drying time of the aliphatic single-component moisture-cured polyurethane adhesive is obviously shortened, the defect that the moisture curing speed of a traditional single-component aliphatic isocyanate prepolymer system is low is overcome, the polarity of the whole structure is improved by introducing the epoxy group, and the compatibility of the modified HDI trimer in the single-component runway adhesive is also improved; meanwhile, unexpectedly, the mechanical property and weather resistance of the polyurethane adhesive are obviously improved after the HDI tripolymer containing imidazoline and epoxy structure is introduced.
The material disclosed by the invention is fast cured outdoors, has excellent mechanical property and weather resistance, and can be used as a bonding material for pavement materials.
In practical use, the single-component polyurethane rubber and EPDM rubber (ethylene propylene diene monomer) particles or other pavement paving materials are mixed according to the mass ratio of 1: 5-6, and paving the mixture on an outdoor road.
The invention has the following beneficial effects:
the single-component polyurethane adhesive overcomes the defect of low moisture curing speed of the traditional single-component aliphatic isocyanate prepolymer system, and improves the mechanical property and weather resistance of the cured adhesive layer; the single-component polyurethane glue is convenient to construct, and the paving material prepared by using the glue is not only yellowing-resistant, but also excellent in mechanical property, weather resistance and the like, and is very suitable for the field of paving outdoor open-air pavements.
Drawings
FIG. 1 is an infrared spectrum of modified hydroxyethyl imidazoline.
Detailed Description
In order to clearly describe the technical solutions and advantages of the present invention, the following further describes the specific embodiments of the present invention, but the present invention is not limited to the embodiments described below.
The raw materials and manufacturers used in the examples of the present invention are described below:
the performance test methods in examples and comparative examples are as follows:
the drying time testing method comprises the steps of preparing the surface of a glue layer sample sheet (or actually paving a glue layer) by touching with a finger, wherein if the hand does not stick, the surface drying is realized, and the time from the beginning of the test to the surface drying is the surface drying time; cutting the glue layer sample sheet (or the actually laid surface layer) by a knife until no inside sticky hand exists, wherein the time from the beginning of the test to the actual drying is the actual drying time (or the curing time);
the tensile strength, the elongation at break and the aging resistance are tested according to the method in GB/T14833-2011;
the rebound rate is tested according to the method in the national standard GB/T1681-;
preparation of modified hydroxyethyl imidazoline:
adding 10g of hydrogen peroxide solution and 5g of formic acid into 500g of oleic acid base hydroxyethyl imidazoline in a dropwise manner, stirring and reacting at 45 ℃ for 2 hours, cooling to room temperature, and finally washing with water, distilling and dehydrating to obtain modified hydroxyethyl imidazoline; 907cm in FIG. 1 -1 The epoxy group characteristic absorption peak appears at the position.
Example 1
Preparation of modified HDI trimer: under the protection of nitrogen, 100gHT-100 g and 217g of modified hydroxyethyl imidazoline are added into a reaction kettle, the mixture is heated to 70 ℃, then is continuously stirred for 2 hours, and after the NCO value is measured by a di-n-butylamine titration method to reach a theoretical value, a modified HDI tripolymer is obtained and then is poured into a closed container for standby;
adding 500gDL-2000D, 20g BDO, 20g TMP and 1g DY-12 catalyst into a reaction kettle, heating to 80 ℃, adding 220g IPDI monomer and 50g modified HDI trimer, reacting for 2.5h, measuring the NCO value to reach the theoretical value, adding 190g plasticizer (epoxy fatty acid methyl ester), continuously stirring for 0.5h, and cooling to obtain the single-component polyurethane adhesive.
Example 2
Preparation of modified HDI trimer: under the protection of nitrogen, 100gHT-100 g and 217g of modified hydroxyethyl imidazoline are added into a reaction kettle, the mixture is heated to 80 ℃, then is continuously stirred for 1h, and after the NCO value is measured by a di-n-butylamine titration method to reach a theoretical value, a modified HDI tripolymer is obtained and then is poured into a closed container for standby;
480gDL-2000D, 30g BDO, 20g TMP and 0.8g DY-12 catalyst are put into a reaction kettle, heated to 80 ℃, added with 190g IPDI monomer and 70g HDI trimer for reaction for 2.5h, added with 210g plasticizer (epoxy fatty acid methyl ester) for continuous stirring for 0.5h after the NCO value reaches the theoretical value, and cooled to obtain the single-component polyurethane adhesive.
Example 3
Preparation of modified HDI trimer: under the protection of nitrogen, 100gHT-100 g and 236.7g of modified hydroxyethyl imidazoline are added into a reaction kettle, the mixture is heated to 75 ℃, then is continuously stirred for 1.5h, and after the NCO value is measured by a di-n-butylamine titration method to reach a theoretical value, modified HDI tripolymer is obtained and then is poured into a closed container for standby;
adding 520gDL-2000D, 25g BDO, 30g TMP and 0.6g DY-12 catalyst into a reaction kettle, heating to 80 ℃, adding 210g IPDI monomer and 60g modified HDI trimer, reacting for 2.5h, measuring NCO value to reach a theoretical value, adding 200g plasticizer epoxy fatty acid methyl ester, continuously stirring for 0.5h, and cooling to obtain the single-component polyurethane adhesive.
Comparative example 1
Adding 500gDL-2000D, 20g BDO, 20g TMP and 1g DY-12 catalyst into a reaction kettle, heating to 80 ℃, adding 220g IPDI monomer, reacting for 2.5h, measuring the NCO value to reach the theoretical value, adding 190g plasticizer (epoxy fatty acid methyl ester), continuously stirring for 0.5h, and cooling to obtain the single-component polyurethane adhesive.
Comparative example 2
480gDL-2000D, 30g BDO, 20g TMP and 0.8g DY-12 catalyst are put into a reaction kettle, heated to 80 ℃, added with 190g IPDI monomer and 70g HDI tripolymer, reacted for 2.5h, measured NCO value reaches the theoretical value, added with 210g plasticizer (epoxy fatty acid methyl ester) and continuously stirred for 0.5h, and cooled to obtain the single-component polyurethane adhesive.
Comparative example 3
Preparation of modified HDI trimer: under the protection of nitrogen, 100gHT-100 g and 94.4g of modified hydroxyethyl imidazoline are added into a reaction kettle, the mixture is heated to 70 ℃, then is continuously stirred for 2 hours, and after the NCO value is measured by a di-n-butylamine titration method to reach a theoretical value, modified HDI tripolymer is obtained and then is poured into a closed container for standby;
adding 520gDL-2000D, 25g BDO, 30g TMP and 0.6g of catalyst DY-12 into a reaction kettle, heating to 80 ℃, adding 210g IPDI monomer and 60g modified HDI trimer, reacting for 2.5h, measuring the NCO value to reach the theoretical value, adding 200g plasticizer (epoxy fatty acid methyl ester), continuing stirring for 0.5h, and cooling to obtain the single-component polyurethane adhesive.
Comparative example 4
Preparation of modified HDI trimer: under the protection of nitrogen, 100-100 gHT g and 208g of oleic hydroxyethyl imidazoline are put into a reaction kettle, heated to 70 ℃, continuously stirred for 2 hours, and poured into a closed container for later use after determining that an NCO value reaches a theoretical value by a di-n-butylamine titration method to obtain a modified HDI tripolymer;
adding 500gDL-2000D, 20g BDO, 20g TMP and 1g DY-12 catalyst into a reaction kettle, heating to 80 ℃, adding 220g IPDI monomer and 50g modified HDI trimer, reacting for 2.5h, measuring the NCO value to reach the theoretical value, adding 190g plasticizer (epoxy fatty acid methyl ester), continuously stirring for 0.5h, and cooling to obtain the single-component polyurethane adhesive.
The single-component adhesive prepared in the above examples and comparative examples and EPDM particles were mixed according to the mass ratio of 1: 5, uniformly mixing, and then paving in a mould, wherein the test performance is shown in the following table 1:
table 1 results of performance test of examples and comparative examples
As can be seen from the above table, after the modified HDI trimer component is introduced into the single-component aliphatic adhesive, on the basis of yellowing resistance, the drying time is obviously shortened in the process of moisture curing, and the mechanical property, the weather resistance and the like are greatly improved.
Finally, it should be noted that the above-mentioned embodiments only illustrate the preferred embodiments of the present invention, and do not limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications can be made by modifying the technical solution of the present invention or equivalent substitutions within the scope of the present invention defined by the claims.
Claims (12)
1. A modified HDI trimer having the structural formula:
2. a method of making the modified HDI trimer of claim 1 comprising the steps of:
(1) oleic acid base hydroxyethyl imidazoline
Mixing hydrogen peroxide and formic acid, and reacting at 45-50 deg.C for 1.5-2h to obtain modified hydroxyethyl imidazoline
(2) Under the protection of nitrogen, HDI tripolymer and modified hydroxyethyl imidazoline react for 1-2 hours at 70-80 ℃, and NCO is measured to reach a theoretical value, so that the modified HDI tripolymer is obtained.
3. The method of claim 2, wherein: the mass ratio of the oleic acid hydroxyethyl imidazoline to the hydrogen peroxide to the formic acid is 50: 12-10: 0.8-0.5.
4. The method of claim 2, wherein: the molar ratio of the HDI tripolymer to the modified hydroxyethyl imidazoline is 1: 1-1.3.
5. The method of claim 2, wherein: the molar ratio of the HDI tripolymer to the modified hydroxyethyl imidazoline is 1: 1.1-1.2.
6. The yellowing-resistant single-component polyurethane adhesive for the pavement paving material comprises the following components: based on 100 parts of the total mass part,
7. the one-component polyurethane adhesive of claim 6, comprising the following components: based on 100 parts of the total mass part,
8. the one-component polyurethane adhesive of claim 6, wherein the aliphatic diisocyanate monomer is selected from one or more of dicyclohexylmethane diisocyanate, isophorone diisocyanate, cyclohexyldimethylene diisocyanate, and hexamethylene diisocyanate.
9. The one-component polyurethane adhesive as claimed in claim 6, wherein the polyether polyol is polypropylene oxide glycol with number average molecular weight of 1500-4000; the chain extender is one of ethylene glycol, 2-methyl-1, 3-propylene glycol, 1, 4-butanediol and diethylene glycol.
10. The one-component polyurethane adhesive of claim 9, wherein the polyether polyol is a polyoxypropylene ether diol having a number average molecular weight of 1800-2200.
11. A method of preparing a one-component polyurethane adhesive according to any one of claims 6 to 10, comprising the steps of: adding polyether polyol, a chain extender, a cross-linking agent and a catalyst into a reaction kettle, heating to 70-80 ℃, adding an aliphatic diisocyanate monomer and a modified HDI trimer, reacting for 2-3h, measuring the NCO value to reach a theoretical value, adding a plasticizer, and continuously stirring for 0.5-1h to obtain the single-component polyurethane adhesive.
12. A road surface paving material comprising the one-component polyurethane rubber of any one of claims 6 to 10 and EPDM rubber in a mass ratio of 1: 5-6.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1027938A1 (en) * | 1997-09-11 | 2000-08-16 | Kansai Paint Co., Ltd. | Method of forming multilayered coating film |
| CN103275666A (en) * | 2013-05-23 | 2013-09-04 | 安徽溢彩玻璃器皿有限公司 | Epoxy resin and polyurethane composite heat transfer printing adhesive and preparation method thereof |
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| US8075857B2 (en) * | 2006-10-18 | 2011-12-13 | Ecolab Usa Inc. | Apparatus and method for making a peroxycarboxylic acid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1027938A1 (en) * | 1997-09-11 | 2000-08-16 | Kansai Paint Co., Ltd. | Method of forming multilayered coating film |
| CN103275666A (en) * | 2013-05-23 | 2013-09-04 | 安徽溢彩玻璃器皿有限公司 | Epoxy resin and polyurethane composite heat transfer printing adhesive and preparation method thereof |
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