CN106590509A - High-viscosity and weather-resistant PUR adhesive and preparing method - Google Patents
High-viscosity and weather-resistant PUR adhesive and preparing method Download PDFInfo
- Publication number
- CN106590509A CN106590509A CN201611094001.2A CN201611094001A CN106590509A CN 106590509 A CN106590509 A CN 106590509A CN 201611094001 A CN201611094001 A CN 201611094001A CN 106590509 A CN106590509 A CN 106590509A
- Authority
- CN
- China
- Prior art keywords
- polyethers
- pur
- polyether polyol
- epoxy resin
- pur adhesives
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of adhesives, in particular to a high-viscosity and weather-resistant PUR adhesive and a preparing method. The adhesive is prepared from 90-115 parts of isophorone diisocyanate, 190-300 parts of polyether polyol, 60-75 parts of epoxy resin and 0.1-0.3 part of a polymerization inhibitor. According to the high-viscosity and weather-resistant PUR adhesive and the preparing method, as the isophorone diisocyanate is used as polyisocyanate, the reaction activity problem is solved, and the yellowing resistance of the product is improved; as the epoxy resin is added, the initial adhesive force of the product can be improved, and the temperature resistance, the weather resistance and the bonding strength of the product can be improved.
Description
Technical field
The present invention relates to adhesive technical field, more particularly to a kind of high viscosity weatherability PUR adhesive and preparation method.
Background technology
PUR adhesives, are a kind of full-bodied wet-solidifying single-component polyurethane adhesives also known as PUR PURs, and its is main
Composition is heterodoxy isocyanate polyurethane performed polymer.PUR adhesives are obtained generally by polyisocyanates with various polyether reactants
Arrive, addition part thickening material, improves the initial adhesion force of PUR adhesives in some products.
Existing PUR adhesives are mostly using methyl diphenylene diisocyanate (MDI) or hexamethylene diisocyanate
(HDI) as polyisocyanates, but it is solid under MDI room temperature, needs cold preservation, self-crosslinking is also easy to produce after baking；HDI toxicity phases
To larger；Also, both polyisocyanates not color inhibitions and reactivity is larger, prepare during PUR adhesives easily
Generation implode, affects the final quality of product.In addition, nylon-based resin is commonly used in current PUR adhesives and improves PUR gluings
The viscosity of agent, and the weatherability of nylon is poor, causes the weatherability of final products poor.
Therefore it provides a kind of viscosity is strong, the strong PUR adhesives of weatherability are necessary.
The content of the invention
First purpose of the present invention is the defect and deficiency existed for prior art, there is provided a kind of high viscosity weatherability
PUR adhesives, specifically adopt the following technical scheme that：
A kind of high viscosity weatherability PUR adhesive, is prepared from by the raw material including following weight portion：
The present invention using isophorone diisocyanate (IPDI) as polyisocyanates, IPDI reactivities less than MDI and
HDI, in course of reaction, can preferably control reaction rate, can be prevented effectively from and the phenomenons such as implode occur；Also, inventor studies
It was found that, due to the use of IPDI, the anti-yellowing property of PUR adhesives can be well improved, product quality is more preferably.
Preferably, the epoxy resin is bisphenol A type epoxy resin, and bisphenol A type epoxy resin strand is longer, belongs to high
Molecular weight elastomers, add the based epoxy resin in the raw material of PUR adhesives, it is possible to increase the cohesive strength of glue-line, make glue
The toughness increase of glutinous agent, impact strength and peel strength are also greatly enhanced.Meanwhile, because containing hydroxyl in bisphenol A type epoxy resin
Base, can form cubic network molecular structure, so except improving the tough of adhesive with the reaction of the isocyano in polyisocyanates
Property outside, can improve the heat resistance of adhesive again, reduce moisture permeability and increase water-resistance.
In a preferred embodiment, the epoxy resin can adopt epoxy resin E-20, commercially available acquisition.
For the IPDI of the present invention, such as reacted using PEPA, then pole-climbing is also easy to produce in course of reaction and is coagulated
Glue phenomenon, product rejection rate is high；Research finds that single employing polyether polyol is reacted with IPDI, can well overcome above-mentioned
Defect, product rejection rate is low, and produces the PUR adhesive viscosities and water-tolerant for obtaining.Wherein, the polyether alcohol can
Selected from material commonly used in the art, present invention preferably employs Propylene Glycol polyoxyethylene ether is (with Propylene Glycol as initiator, with epoxy third
Ring ring-opening polymerisation is formed), such polyethers is cheap, simple to operate, and by adjusting the consumption of polyethers, can control the viscous of product
Degree scope is 3000-25000mPa.s, can meet various demands of the client to viscosity.
It is further preferred that the molecular weight of the polyether polyol is 400-2500, and/or, the polyether polyol
Hydroxyl value is 50-300.
The polyether polyol can adopt commercially available polyethers N220, polyethers N2070 and polyethers N204.Wherein, polyethers N220
Molecular weight be 200, hydroxyl value is 56.1；The molecular weight of polyethers 2070 is 700, and hydroxyl value is 238；The molecular weight of polyethers N204 is
400, hydroxyl value is 280.5.
Preferably, in the polyether polyol, the weight ratio of polyethers N220, polyethers N2070, polyethers N204 is (3～8)：
1：(0.8～2).In a particular embodiment, the consumption of polyethers N220 can be 140-220 parts, and the consumption of polyethers N2070 can be
30-45 parts, the consumption of polyethers N204 can be 22-35 parts.
Due to polyether polyol, reactivity is larger during PUR is prepared, therefore, the present invention adds polymerization inhibitor to drop
The speed of oligomerizing, makes reaction slowly carry out, it is ensured that the quality of product.Wherein, the polymerization inhibitor can be public using this area
One or more in the material known, such as phosphoric acid, hydroquinone, p-tert-Butylcatechol, tert-butylhydroquinone, research
It was found that, for the reaction system of the present invention, there is optimal polymerization inhibition effect as polymerization inhibitor using phosphoric acid, the product for obtaining it is viscous
Degree, weatherability, color inhibition effect are best, and compared with other polymerization inhibitors, phosphoric acid is nontoxic, safe operation.
Preferably, the phosphoric acid refers to the phosphate aqueous solution that mass concentration is 80-90% (preferably 85%).
Used as the technical scheme that the present invention is optimal, PUR adhesives are prepared from by the raw material including following weight portion：
Second object of the present invention is to provide the preparation method of above-mentioned PUR adhesives, specially：Inert gas shielding
Under, make isophorone diisocyanate, polyether polyol and polymerization inhibitor in 60-80 DEG C of reaction, epoxy resin is subsequently adding in 80-
90 DEG C of reactions, obtain final product.
When the polyether polyol is polyethers N220, polyethers N2070 and polyethers N204, because different polyether reactants is lived
Property it is different, therefore, the addition sequence and response time for controlling polyethers can regulate and control the speed of reaction and the strand of product, it is ensured that
The performance of final product.Present invention preferably employs following method adds polyethers to prepare target product：Under inert gas shielding, first make
Isophorone diisocyanate is with polyethers N220 and phosphoric acid reacts 0.5-1.5h in 60-75 DEG C, is subsequently adding polyethers N2070, in
60-75 DEG C reaction 0.5-1.5h, add polyethers N204, in 60-75 DEG C react 1.5-2.5h, be eventually adding epoxy resin in
80-90 DEG C of reaction 10-40min, obtains final product.
The optimal preparation method of the present invention is：Under inert gas shielding, isophorone diisocyanate and polyethers are first made
N220 and phosphoric acid react 1h in 70 DEG C, are subsequently adding polyethers N2070, and in 70 DEG C 1h is reacted, and add polyethers N204, anti-in 70 DEG C
2h is answered, epoxy resin is eventually adding and is reacted 30min in 85 DEG C, obtained final product.
On the basis of common sense in the field is met, above-mentioned each optimum condition can be mutually combined, and obtain final product the present invention each preferably
Example.
The unit of weights such as the μ g that " weight portion " of the present invention is known in the art, mg, g, kg, or for its multiple, such as
1/10,1/100,10 times, 100 times etc..
The present invention relates to the commercially available acquisition of raw material and reagent.
The present invention achieves following good effect：Compared with prior art, the present invention adopted IPDI for polyisocyanates, both
Reactivity is solved the problems, such as, the anti-yellowing property of product is improve again；Epoxy resin is added both to improve the first glutinous of product
Power, improves temperature tolerance, weatherability and the adhesion strength of product again.
Description of the drawings
Fig. 1 is the process route chart of preparation method of the present invention.
Specific embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.The operation being related in embodiment
If no special instructions, it is this area customary technical operation.
Embodiment 1
A kind of high viscosity weatherability PUR adhesive, is prepared from by the raw material of following weight：
Embodiment 2
A kind of esters of acrylic acid color inhibition PUR adhesives, are prepared from by the raw material of following weight：
Embodiment 3
A kind of esters of acrylic acid color inhibition PUR adhesives, are prepared from by the raw material of following weight：
Embodiment 4
The embodiment provides the preparation method of any one PUR adhesive of embodiment 1-3, and technological process is as shown in figure 1, concrete
For：Under nitrogen protection, first make isophorone diisocyanate with polyethers N220 and phosphoric acid reacts 1h in 70 DEG C, be subsequently adding polyethers
N2070, in 70 DEG C 1h is reacted, and adds polyethers N204, and in 70 DEG C 2h is reacted, and is eventually adding epoxy resin in 85 DEG C of reactions
30min, obtains final product.
Effect experimental
With HG-2690B bulb-type non-yellowing test machines, the sample of embodiment 1-3 is put in equipment and is irradiated, 200 hours
Without yellowing.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
State, but on the basis of the present invention, it can be made some modifications or improvements, this is to those skilled in the art apparent
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Scope.
Claims (10)
1. a kind of high viscosity weatherability PUR adhesive, it is characterised in that：It is prepared from by the raw material including following weight portion：
2. PUR adhesives according to claim 1, it is characterised in that：The epoxy resin is bisphenol A type epoxy resin.
3. PUR adhesives according to claim 1 and 2, it is characterised in that：The polyether polyol is Propylene Glycol polyoxy second
Alkene ether.
4. PUR adhesives according to claim 3, it is characterised in that：The molecular weight of the polyether polyol is 400-
2500；And/or, the hydroxyl value of the polyether polyol is 50-300.
5. PUR adhesives according to claim 3, it is characterised in that：The polyether polyol is selected from polyethers N220, polyethers
N2070, one or more in polyethers N204, preferably three kinds.
6. PUR adhesives according to claim 5, it is characterised in that：In the polyether polyol, polyethers N220, polyethers
The weight ratio of N2070, polyethers N204 is (3～8)：1：(0.8～2).
7. PUR adhesives according to claim 1 or 2 or 6, it is characterised in that：The polymerization inhibitor is selected from phosphoric acid, to benzene two
One or more in phenol, p-tert-Butylcatechol, tert-butylhydroquinone, preferably phosphoric acid, more preferably matter
The phosphate aqueous solution of amount concentration 80-90%.
8. PUR adhesives according to claim 1, it is characterised in that：It is prepared from by the raw material including following weight portion：
9. a kind of method for preparing PUR adhesives described in any one of claim 1-8, it is characterised in that：Under inert gas shielding,
Make isophorone diisocyanate, polyether polyol and polymerization inhibitor in 60-80 DEG C of reaction, be subsequently adding epoxy resin in 80-90
DEG C reaction, obtain final product.
10. method according to claim 9, it is characterised in that：Under inert gas shielding, isophorone diisocyanate is first made
Ester is with polyethers N220 and phosphoric acid reacts 0.5-1.5h in 60-75 DEG C, is subsequently adding polyethers N2070, and in 60-75 DEG C 0.5- is reacted
1.5h, adds polyethers N204, and in 60-75 DEG C 1.5-2.5h is reacted, and is eventually adding epoxy resin and reacts 10- in 80-90 DEG C
40min, obtains final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611094001.2A CN106590509A (en) | 2016-12-01 | 2016-12-01 | High-viscosity and weather-resistant PUR adhesive and preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611094001.2A CN106590509A (en) | 2016-12-01 | 2016-12-01 | High-viscosity and weather-resistant PUR adhesive and preparing method |
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| Publication Number | Publication Date |
|---|---|
| CN106590509A true CN106590509A (en) | 2017-04-26 |
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|---|---|---|---|
| CN201611094001.2A Pending CN106590509A (en) | 2016-12-01 | 2016-12-01 | High-viscosity and weather-resistant PUR adhesive and preparing method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109468112A (en) * | 2018-10-30 | 2019-03-15 | 北京华腾新材料股份有限公司 | A kind of high speed compound low-residual high temperature resistance and high strength polyether polyurethane adhesive and preparation method thereof |
| CN111976241A (en) * | 2020-08-13 | 2020-11-24 | 福建思嘉环保材料科技有限公司 | Environment-friendly space cloth material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594481A (en) * | 2004-06-24 | 2005-03-16 | 淄博海特曼化工有限公司 | Solvent-free high-strength polyurethane cementing sealing glue and method for making same |
-
2016
- 2016-12-01 CN CN201611094001.2A patent/CN106590509A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594481A (en) * | 2004-06-24 | 2005-03-16 | 淄博海特曼化工有限公司 | Solvent-free high-strength polyurethane cementing sealing glue and method for making same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109468112A (en) * | 2018-10-30 | 2019-03-15 | 北京华腾新材料股份有限公司 | A kind of high speed compound low-residual high temperature resistance and high strength polyether polyurethane adhesive and preparation method thereof |
| CN109468112B (en) * | 2018-10-30 | 2021-09-14 | 北京华腾新材料股份有限公司 | Low-residue high-temperature-resistant high-strength polyether polyurethane adhesive for high-speed compounding and preparation method thereof |
| CN111976241A (en) * | 2020-08-13 | 2020-11-24 | 福建思嘉环保材料科技有限公司 | Environment-friendly space cloth material and preparation method thereof |
| CN111976241B (en) * | 2020-08-13 | 2023-10-10 | 福建思嘉环保材料科技有限公司 | Environment-friendly space cloth material and preparation method thereof |
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