CN106700884A - PUR adhesive and preparation method - Google Patents

PUR adhesive and preparation method Download PDF

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Publication number
CN106700884A
CN106700884A CN201611088558.5A CN201611088558A CN106700884A CN 106700884 A CN106700884 A CN 106700884A CN 201611088558 A CN201611088558 A CN 201611088558A CN 106700884 A CN106700884 A CN 106700884A
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CN
China
Prior art keywords
pur adhesives
pur
adhesives according
raw material
polyethers
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
Application number
CN201611088558.5A
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Chinese (zh)
Inventor
胡凤娇
曹建强
张军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dimma New Material Technology (suzhou) Co Ltd
Original Assignee
Dimma New Material Technology (suzhou) Co Ltd
Priority date (The priority date 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 date listed.)
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Application filed by Dimma New Material Technology (suzhou) Co Ltd filed Critical Dimma New Material Technology (suzhou) Co Ltd
Priority to CN201611088558.5A priority Critical patent/CN106700884A/en
Publication of CN106700884A publication Critical patent/CN106700884A/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/757—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 at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to the technical field of adhesives, in particular to a PUR adhesive and a preparation method. The adhesive is prepared from, by weight, 20-25 parts of cyclohexane dimethylene diisocyanate, 2-7 parts of 2,2,4-trimethylhexane diisocyanate, 60-85 parts of polyether polyol, 2-4 parts of polyester polyol, 0.01-0.1 part of polymerization inhibitor and 0.05-0.1 part of catalyst. Cyclohexane dimethylene diisocyanate and 2,2,4-trimethylhexane diisocyanate are polyisocyanates, do not crystallize at normal temperature, are not likely to be self-crosslinked at normal temperature and are good in storage stability; the raw material refrigeration cost and the raw material heating and dissolving cost are reduced. The PUR adhesive has good yellowing resistance, light resistance, weather resistance and flexibility.

Description

A kind of PUR adhesives and preparation method
Technical field
The present invention relates to adhesive technical field, more particularly to a kind of PUR adhesives 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 a kind of plastic type adhesives, in certain temperature range its Physical state is varied with temperature and changed, and chemical characteristic is constant, and its is nonpoisonous and tasteless, is solid state under normal temperature, belongs to environment-friendly type Chemical products.PUR adhesives are obtained generally by polyisocyanates with various polyether reactants.The original of existing PUR adhesives The general easily crystallization of material is, it is necessary to Cord blood, uses after baking and easily produce self-crosslinking, the PUR PURs prepared by it again Do not possess yellowing resistance, light resistance, weatherability is also poor, cannot preferably take into account pliability yet.Therefore it provides a kind of with resistance to Xanthochromia performance, light resistance, weatherability, PUR adhesives that pliability is good it is necessary.
The content of the invention
First purpose of the invention is directed to the defect and deficiency of prior art presence, there is provided a kind of PUR adhesives, tool Body is adopted the following technical scheme that：
A kind of PUR adhesives, are prepared from by the raw material including following weight portion：
The present invention is not easy to produce self-crosslinking from crystallization is difficult under normal temperature, sub- without baking also easy-operating hexamethylene two Methyl diisocyanate (HXDI) and 2,2,4- trimethylhexane diisocyanates (TMHDI) as PUR adhesives raw material, by Particularity in the two on molecular structure, preparation-obtained PUR adhesives have preferable light resistance, weatherability and resistance to Xanthochromia.The pliability of PUR adhesives of the present invention can be improved by adjusting the ratio of HXDI and TMHDI.Specifically, when The mol ratio of HXDI and TMHDI is 4：1~9：When 1, with preferably pliability；When the two molar ratio is 4：1 and 9：When 1, The PUR adhesives for obtaining have optimal pliability.
In above-mentioned adhesive, the PPG may be selected from material commonly used in the art, and currently preferred polyethers is more First alcohol is the mixture of PolyTHF polyethers and propane diols APEO.Wherein, PolyTHF polyethers is prepared Polyurethane has modulus and elasticity higher, excellent water resistance, wear-resisting, resistance to mould, oil resistivity, and excellent dynamic property And low temperature flexibility, but PolyTHF polyethers is relatively costly, therefore, the present invention uses PolyTHF polyethers and propane diols polyoxy The mode of vinethene compounding use, entreprise cost can be reduced on the premise of product combination property is ensured.
Preferably, the molecular weight of the PolyTHF polyethers is 1800-3000.
Preferably, the hydroxyl value of the PolyTHF polyethers is 35-60.
Preferably, the molecular weight of the propane diols APEO is 400-800.
Preferably, the hydroxyl value of the propane diols APEO is 110-300.
In a particular embodiment, it is 1 that the propane diols APEO is preferably weight ratio：The polyethers of (1-2) 2070 and the mixture of polyethers 400.
Preferably, the hydroxyl value of the PEPA is 1800-2500.
Preferably, the acid number of the PEPA is less than 1mgKOH/g.
Preferably, the hydroxyl value of the PEPA is 40-60.
In a particular embodiment, the type product of polyester 2000 can be used.
In above-mentioned adhesive, the polymerization inhibitor can use material commonly used in the art, present invention preferably employs phosphoric acid, phosphoric acid The reaction rate of different hydracid root and hydroxyl can be slowed down, it is ensured that the final performance of product.Further preferably use mass concentration for 85% phosphate aqueous solution is used as polymerization inhibitor.
In above-mentioned adhesive, the catalyst can use material commonly used in the art, present invention preferably employs stannous octoate And/or dibutyl tin laurate, most preferably using dibutyl tin laurate, dibutyl tin laurate is a kind of strong gel The catalyst of property, and with good heat endurance, the stabilization of product is can further ensure that as catalyst of the invention Property.
Used as the present invention preferably technical scheme, PUR adhesives are prepared from by the raw material including following weight portion：
Or,
Used as the technical scheme that the present invention is optimal, PUR adhesives are prepared from by the raw material including following weight portion：
Or,
Second object of the present invention is to provide the preparation method of above-mentioned any one PUR adhesive, specially：Indifferent gas Under body protection, in 55-65 DEG C, by cyclohexanedimethyleterephthalate diisocyanate, 2,2,4- trimethylhexane diisocyanates and resistance Poly- agent is well mixed, and is subsequently adding PPG in 75-85 DEG C of reaction, is eventually adding PEPA and catalyst, continues In 75-85 DEG C of reaction, obtain final product.
Preferably preparation method of the invention is：Under inert gas shielding, in 60 DEG C, by the isocyanic acid of cyclohexanedimethyleterephthalate two Ester, 2,2,4- trimethylhexane diisocyanates and polymerization inhibitor are well mixed, and are subsequently adding PPG and are reacted in 80 DEG C, most PEPA and catalyst are added afterwards, 80 DEG C of reactions are continued at, and are obtained final product.
The isocyano-content of PUR adhesives of the present invention is 3.5%~4.5%.
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 present invention relates to the commercially available acquisition of raw material and reagent.
The present invention achieves following good effect：It is polyisocyanates that the present invention uses HXDI and TMHDI, both materials Do not crystallize at normal temperatures and be not easy to produce self-crosslinking, storage stability is good, save raw material refrigeration cost and raw material heating is molten The cost of solution, PUR adhesives of the invention have good anti-yellowing property, light resistance, weatherability and pliability.
Brief description of the drawings
Fig. 1 is the preparation technology flow chart of PUR adhesives 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 Unless otherwise specified, it is this area customary technical operation.
Embodiment 1
A kind of PUR adhesives, are prepared from by the raw material of following weight：
Embodiment 2
A kind of PUR adhesives, are prepared from by the raw material of following weight：
Embodiment 3
The embodiment provides the preparation method of PUR adhesives described in embodiment 1, and process chart refer to Fig. 1, specifically For：Under inert gas shielding, in 60 DEG C, by cyclohexanedimethyleterephthalate diisocyanate, 2, the isocyanic acid of 2,4- trimethyl cyclohexane two Ester and polymerization inhibitor are well mixed, are subsequently adding the PolyTHF polyethers of dehydration, and polyethers 2070, polyethers 400 reacts in 80 DEG C, Polyester 2000 and phosphoric acid are eventually adding, 80 DEG C of reactions are continued at, obtained final product.
The preparation method of PUR adhesives is same described in embodiment 2.
Anti-yellowing property
With HG-2690B bulb-type non-yellowing test machines, the sample of embodiment 1-2 is put into equipment and is irradiated, 200 hours Without yellowing.
Although above having used general explanation, specific embodiment and experiment, 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 PUR adhesives, are prepared from by the raw material including following weight portion：
2. PUR adhesives according to claim 1, it is characterised in that：Cyclohexanedimethyleterephthalate diisocyanate and 2,2, The mol ratio of 4- trimethylhexane diisocyanates is (4~9)：1；Preferably 9：1 or 4：1.
3. PUR adhesives according to claim 1 and 2, it is characterised in that：The PPG is poly- for PolyTHF The mixture of ether and propane diols APEO.
4. PUR adhesives according to claim 3, it is characterised in that：The molecular weight of the PolyTHF polyethers is 1800-3000；And/or, the hydroxyl value of the PolyTHF polyethers is 35-60.
5. PUR adhesives according to claim 3, it is characterised in that：The molecular weight of the propane diols APEO is 400-800；And/or, the hydroxyl value of the propane diols APEO is 110-300；
Preferably, the propane diols APEO is that weight ratio is 1：The polyethers 2070 of (1-2) and the mixture of polyethers 400.
6. PUR adhesives according to claim 1 or 2 or 4 or 5, it is characterised in that：The hydroxyl value of the PEPA is 1800-2500；And/or, the acid number of the PEPA is less than 1mgKOH/g；And/or, the hydroxyl value of the PEPA is 40-60。
7. PUR adhesives according to claim 1, it is characterised in that：The polymerization inhibitor is phosphoric acid；And/or, the catalysis Agent is stannous octoate and/or dibutyl tin laurate.
8. PUR adhesives according to claim 1, it is characterised in that：It is prepared from by the raw material including following weight portion：
Or,
9. PUR adhesives according to claim 8, it is characterised in that：It is prepared from by the raw material including following weight portion：
Or,
10. the preparation method of PUR adhesives described in any one of claim 1-9, it is characterised in that：Under inert gas shielding, in 55-65 DEG C, by cyclohexanedimethyleterephthalate diisocyanate, 2,2,4- trimethylhexane diisocyanates and polymerization inhibitor mixing are equal It is even, PPG is subsequently adding in 75-85 DEG C of reaction, PEPA and catalyst are eventually adding, continue at 75-85 DEG C instead Should, obtain final product.
CN201611088558.5A 2016-12-01 2016-12-01 PUR adhesive and preparation method Pending CN106700884A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108530597A (en) * 2018-04-04 2018-09-14 南京双威生物医学科技有限公司 Resistance to ultraviolet water cure performed polymer of one kind and its preparation method and application
CN112662359A (en) * 2020-12-17 2021-04-16 浙江枧洋高分子科技有限公司 Moisture-cured polyurethane hot melt adhesive and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102838963A (en) * 2012-09-13 2012-12-26 张明利 Preparation method of high-temperature anti-yellowing polyurethane adhesive size

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102838963A (en) * 2012-09-13 2012-12-26 张明利 Preparation method of high-temperature anti-yellowing polyurethane adhesive size

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘益军: "《聚氨酯原料及助剂手册 第二版》", 31 January 2013, 化学工业出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108530597A (en) * 2018-04-04 2018-09-14 南京双威生物医学科技有限公司 Resistance to ultraviolet water cure performed polymer of one kind and its preparation method and application
CN112662359A (en) * 2020-12-17 2021-04-16 浙江枧洋高分子科技有限公司 Moisture-cured polyurethane hot melt adhesive and preparation method thereof

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Application publication date: 20170524