CN106520054A - Low-friction-coefficient and solvent-free type polyurethane adhesive and preparation method thereof - Google Patents
Low-friction-coefficient and solvent-free type polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN106520054A CN106520054A CN201611007827.0A CN201611007827A CN106520054A CN 106520054 A CN106520054 A CN 106520054A CN 201611007827 A CN201611007827 A CN 201611007827A CN 106520054 A CN106520054 A CN 106520054A
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- polyester polyol
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- 239000000853 adhesive Substances 0.000 title claims abstract description 57
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 57
- 239000004814 polyurethane Substances 0.000 title claims abstract description 10
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 27
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 78
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 15
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims description 29
- 150000003077 polyols Chemical class 0.000 claims description 29
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 22
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 claims description 20
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 19
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 18
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 14
- 235000011037 adipic acid Nutrition 0.000 claims description 11
- 239000001361 adipic acid Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229960004063 propylene glycol Drugs 0.000 claims description 11
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 9
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- 150000007519 polyprotic acids Polymers 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 5
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 5
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- -1 carbodiimide modified MDI Chemical class 0.000 claims description 3
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims 4
- 239000002131 composite material Substances 0.000 abstract description 32
- 239000012790 adhesive layer Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract 2
- 230000003068 static effect Effects 0.000 description 19
- 239000000463 material Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000009459 flexible packaging Methods 0.000 description 7
- 238000013329 compounding Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012858 packaging process Methods 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005903 polyol mixture Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Classifications
-
- 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
- C09J175/06—Polyurethanes from polyesters
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
Landscapes
- 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 discloses low-friction-coefficient and solvent-free type polyurethane adhesive and a preparation method thereof and belongs to the field of polyurethane adhesive preparation. The adhesive is prepared from A component and B component, wherein the A component is prepared from modified polyester polyol and polyisocyanate which react with each other, and the B component is prepared from modified polyester polyol. By means of molecular design, the appropriate proportion of branched chain is introduced into the adhesive; thus, the regularity of the adhesive is reduced, a solidified adhesive layer of the adhesive has certain microcosmic unevenness, the microcosmic unevenness of a composite membrane is further obtained, the bonding force between surfaces is reduced, and the composite membrane has a low friction coefficient; as the branched chain is introduced into the adhesive, the crystalline of the molecular chain is reduced, the transparency of the adhesive is improved, the adhesive also can obtain lower viscosity and good coating performance, and the adhesive is wider in application range in the field of composite flexible package. The solvent-free adhesive has no solvent residue and is high in safety.
Description
Technical Field
The invention relates to the field of preparation of polyurethane adhesives, in particular to a solvent-free polyurethane adhesive with low friction coefficient for composite flexible packages in the fields of food, daily necessities, medicines and the like and a preparation method thereof.
Background
The solvent-free polyurethane adhesive for the composite flexible package has outstanding environmental protection and safety, has outstanding advantages of low cost, low energy consumption, stable composite film quality, high composite efficiency and the like, is widely concerned, has increasingly wide application range, and can be applied to various composite flexible packages such as food, daily necessities, medicines, agricultural products, industrial products, cosmetics, electronic products and the like.
Solvent-free composite adhesives have been widely used, however, the problem of high coefficient of friction of flexible packaging composite films is often encountered during the application of solvent-free adhesives.
The coefficient of friction is one of the basic properties of various materials. When there is relative motion or relative motion trend between two objects in contact with each other, the mechanical force generated on the contact surface of the two objects to resist the relative motion is friction. The friction performance of a certain material can be characterized by the static and dynamic friction coefficients of the material. The static friction force is the maximum resistance of the two contact surfaces at the beginning of the relative movement, and the ratio of the resistance to the normal force is the static friction coefficient; the kinetic friction force is the resistance of two contact surfaces moving relatively at a certain speed, and the ratio of the kinetic friction force to the normal force is the kinetic friction coefficient.
The coefficient of friction is an index for measuring the sliding properties of the packaging material, and it is very important for the film packaging process that the surface of the film material is smooth and has a proper coefficient of friction, and different requirements are imposed on the coefficient of friction for producing packaging material products for different purposes. The friction force in the actual packaging process is often both drag and drag, and therefore the magnitude of the coefficient of friction must be effectively controlled to be within a suitable range. If the friction coefficient is too large, if the friction coefficient of the composite film exceeds 0.3, the composite film can be pulled immovably on a bag making machine; if the coefficient of friction of the pouch-making product exceeds 0.25, some flexible packaging bags are liable to have poor opening.
It has been found that the coefficient of friction of flexible packaging composite films is related to a number of factors: the method is related to the surface roughness, the dry and wet degree and the surface temperature of a raw material film, and is related to an adhesive for compounding, a compounding process, a curing process, a bag making/automatic packaging process, the temperature and the humidity of a testing environment and the like.
The friction coefficient of the composite film is high, and the friction force on a bag making machine is large, so that the composite film is immovable, seriously stretched and even difficult to make a bag, or the flexible packaging composite bag is unsmooth and cannot be opened, thereby causing troubles to subsequent processes. These phenomena are more pronounced when the inner layer is a PE film, particularly a thin PE film, which, however, is the most used inner layer of a flexible packaging laminate film.
Disclosure of Invention
Based on the problems in the prior art, the invention aims to provide a solvent-free polyurethane adhesive with a low friction coefficient and a preparation method thereof, and the convenience of manufacturing a composite flexible package on a bag making machine is improved.
The purpose of the invention is realized by the following technical scheme:
the embodiment of the invention provides a solvent-free polyurethane adhesive with a low friction coefficient, which consists of a component A and a component B, wherein the molar ratio of functional groups of the component A to the component B is as follows: -NCO: -OH ═ 1.1 to 1.8: 1; wherein,
the component A adopts a modified isocyanate addition product formed by reacting modified polyester polyol with polyisocyanate;
the component B adopts modified polyester polyol.
The embodiment of the invention provides a preparation method of a solvent-free polyurethane adhesive with a low friction coefficient, which is used for preparing the adhesive of any one of claims 1 to 9 and comprises the following steps:
respectively preparing modified polyester polyol of the component A and modified polyester polyol of the component B according to the formula of the adhesive;
preparing a component A: adding polyisocyanate, keeping the temperature of the kettle at 25-35 ℃, adding the prepared modified polyester polyol, reacting for 3-4 hours at 70-80 ℃, and cooling to normal temperature to obtain a component A;
the prepared component A and component B are prepared according to the molar ratio of functional groups as follows: -NCO: -OH ═ 1.1 to 1.8: 1, namely the solvent-free polyurethane adhesive is formed by matching.
According to the technical scheme provided by the invention, the A, B components of the adhesive are modified polyester polyol, branched chains are introduced into the modified polyester polyol, and the branched chains with proper proportion are introduced through molecular design, so that the regularity of the adhesive can be reduced, the cured adhesive layer of the adhesive has certain microscopic unevenness, the composite film has the microscopic unevenness, the bonding force between the surface and the surface is reduced, the composite film has low friction coefficient, and the solvent-free type bi-component polyurethane adhesive with low friction coefficient is prepared; and through the introduction of the branched chain, the crystallinity of a molecular chain can be reduced, the transparency of the adhesive is improved, and the adhesive can obtain lower viscosity and good coating performance, so that the adhesive has a wider application range in the field of composite flexible packaging.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a solvent-free polyurethane adhesive with a low friction coefficient, which consists of a component A and a component B, wherein the molar ratio of functional groups of the component A to the component B is as follows: -NCO: -OH ═ 1.1 to 1.8: 1; wherein,
the component A adopts a modified isocyanate addition product formed by reacting modified polyester polyol with polyisocyanate;
the component B adopts modified polyester polyol.
In the adhesive, the mass percentage of NCO% of the component A is 8% -21%.
In the adhesive, the polyester polyols in the component A and the component B are both synthesized by micromolecular polyol and micromolecular polybasic acid.
In the adhesive, the polyester polyol in the component A and the component B is synthesized by micromolecular polyol and micromolecular polybasic acid in the following way:
the mol ratio of the small molecular polyol to the small molecular polyacid is as follows: -OH: -COOH ═ 1.2 to 1.8: 1.0, and obtaining the polyester polyol after reaction.
In the adhesive, the small molecular polyol adopted in the polyester polyol of the component A is selected from the following components: at least one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, 2-dimethyl-1, 3-propylene glycol, 1, 4-butanediol, 1, 2-pentanediol, 1, 5-pentanediol, 2-methyl-2, 4-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol;
the small molecular polyol adopted in the polyester polyol of the component B is selected from the following components: at least one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, 2-dimethyl-1, 3-propylene glycol, 1, 4-butanediol, 1, 2-pentanediol, 1, 5-pentanediol, 2-methyl-2, 4-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, glycerol, and trimethylolpropane.
In the adhesive, the polyester polyol of the component A at least comprises one of 1, 2-propylene glycol, 2-methyl-1, 3-propylene glycol, 2-dimethyl-1, 3-propylene glycol, 1, 2-pentanediol and 2-methyl-2, 4-pentanediol in small molecular polyol, and the using amount of the small molecular polyol accounts for 30-100% of the total mole number of the small molecular polyol;
the polyester polyol of the component B at least comprises one of 1, 2-propylene glycol, 2-methyl-1, 3-propylene glycol, 2-dimethyl-1, 3-propylene glycol, 1, 2-pentanediol, 2-methyl-2, 4-pentanediol, glycerol and trimethylolpropane in the small molecular polyol, wherein the amount of the small molecular polyol is 30-100% of the total molar number of the small molecular polyol.
In the adhesive, the polyester polyol of the component B also at least comprises one of glycerol and trimethylolpropane in the micromolecular polyol, and the using amount of the micromolecular polyol accounts for 0.1-5% of the total mole number of the micromolecular polyol.
In the adhesive, the small molecular polybasic acid adopted in the polyester polyol of the component A is selected from the following components: at least one of adipic acid and sebacic acid;
the small molecular polybasic acid adopted in the polyester polyol of the component B is selected from the following groups: at least one of adipic acid, sebacic acid, isophthalic acid, terephthalic acid, phthalic anhydride.
In the adhesive, the polyisocyanate in the component A is selected from the following components:
the mixture of diphenylmethane-4, 4 '-diisocyanate, diphenylmethane-4, 4' -diisocyanate and diphenylmethane-2, 4 '-diisocyanate, wherein the weight ratio of 2, 4' isomer in the mixture is more than or equal to 25%, and at least one of polyether modified MDI, carbodiimide modified MDI, polymethylene polyphenyl polyisocyanate and isophorone diisocyanate.
In the above adhesive, the polyester polyol of the B component may further include: and polycaprolactone diol or polycaprolactone triol accounting for 0.1-30% of the total weight of the component B.
The embodiment of the invention also provides a preparation method of the solvent-free polyurethane adhesive with low friction coefficient, which comprises the following steps:
respectively preparing modified polyester polyol of the component A and modified polyester polyol of the component B according to the formula of the adhesive;
preparing a component A: adding polyisocyanate, keeping the temperature of the kettle at 25-35 ℃, adding the prepared modified polyester polyol, reacting for 3-4 hours at 70-80 ℃, and cooling to normal temperature to obtain a component A;
the prepared component A and component B are prepared according to the molar ratio of functional groups as follows: -NCO: -OH ═ 1.1 to 1.8: 1, namely the solvent-free polyurethane adhesive is formed by matching.
When two surfaces are contacted with each other, a strong bonding force, namely static friction force, is formed at the contact place between the two surfaces when the two surfaces are static, the bonding force is not broken, one surface can move towards the other surface, the force for breaking the bonding force is broken, and the ratio of the vertical force to one surface is called the static friction coefficient. According to modern friction theory, friction is caused by the adhesion between the atoms of the contacting surfaces, when two objects are in contact with each other, first the atoms of the surface of the raised portion are relatively close to form atomic bonds, the strength of which is comparable to the strength of atomic bonds inside a solid which bring itself together. If the surfaces are very clean and in close contact, the two surfaces in contact with each other will adhere very firmly, with a high friction, even exceeding a positive pressure, and a coefficient of friction equal to, greater than 1, or even greater.
According to the modified polyester polyol used in the A, B component, through the design of a molecular structure, branched chains with a proper proportion are introduced into the polyester polyol, and the branched chains can reduce the regularity of an adhesive, so that a cured adhesive layer of the adhesive has certain microscopic unevenness, the bonding force between the surface and the surface is reduced, and the composite film has a low friction coefficient when the modified polyester polyol is used in the composite film. In the polyurethane adhesive, the component A is an addition product of modified isocyanate formed by reacting modified polyester polyol with polyisocyanate, and the component B is modified polyester polyol. Because the component A and the component B both use the modified polyester polyol, the modified polyester polyol can not absorb the slipping agent in the raw material film, has little influence on the friction coefficient of the composite film, can ensure that the composite film obtains low friction coefficient, and can obviously reduce the static friction coefficient and the dynamic friction coefficient of the flexible packaging composite film, thereby ensuring that the composite film can be smoothly made into bags and has good openness, and solving the problems of high friction coefficient, difficult bag making or difficult opening of the current common solvent-free adhesive. And the solvent-free adhesive has no solvent residue and high safety.
The embodiments of the present invention will be described in further detail with reference to specific examples.
Example one
The embodiment provides a solvent-free two-component polyurethane adhesive, which consists of A, B components, wherein the A component is formed by reacting modified polyester polyol with polyisocyanate and is an addition product of modified isocyanate; the component B is polyester polyol which is modified polyol;
the A component and the B component can be prepared from the following components in a functional group molar ratio: -NCO: -OH ═ 1.54: 1.0 to form the adhesive.
The preparation method of the adhesive comprises the following steps:
firstly, preparing a component A:
firstly, preparing polyester polyol, comprising:
(1) raw materials: 0.5mol of 2-methyl-2, 4-pentanediol, 0.8mol of 1, 6-hexanediol, 0.8mol of adipic acid, 0.2mol of sebacic acid;
(2) the preparation method comprises the following steps:
adding all small molecular weight polyol (namely 0.5mol of 2-methyl-2, 4-pentanediol and 0.8mol of 1, 6-hexanediol) into a polyester reaction kettle, and uniformly mixing to form a small molecular weight polyol mixture; heating to 60 ℃, adding 0.8mol of adipic acid and 0.2mol of sebacic acid, closing a feeding cover, continuing heating, starting stirring, and introducing nitrogen; and (3) beginning to discharge water when the temperature in the kettle reaches about 130 ℃, controlling the temperature at the top of the fractionating tower to be 100-102 ℃, continuously heating the reaction kettle, and discharging theoretical water when the temperature in the kettle reaches about 230 ℃. After the water is discharged, preserving the heat for 2 hours, and stopping introducing the nitrogen;
sampling to test the acid value, and controlling the acid value to be below 25; the temperature in the kettle is kept at 230 ℃ and 250 ℃, the kettle is gradually vacuumized, and the hydroxyl value and the acid value are tested, wherein the hydroxyl value reaches 95 +/-6, and the acid value is 0.3-1 qualified; cooling and discharging to prepare the polyester polyol with the hydroxyl value of 92 and the acid value of 0.8.
(II) synthesizing a component A (the using amount of each component is in parts by weight):
(1) preparing materials: 45 parts of the above polyester polyol, 55 parts of C-MDI;
(2) the preparation method comprises the following steps:
adding 55 parts of C-MDI, keeping the kettle temperature at 25-35 ℃, adding 45 parts of polyester polyol, reacting for 3 hours at 70 ℃, and cooling to normal temperature to obtain the component A. Test a component NCO% ═ 12.6%.
Secondly, preparing a component B:
preparing a polyester polyol comprising:
(1) preparing materials: 0.8mol of triethylene glycol, 0.4mol of 2-methyl-1, 3-propanediol, 0.3mol of 2, 2-dimethyl-1, 3-propanediol, 0.03mol of glycerol, 0.85mol of adipic acid and 0.15mol of isophthalic acid;
(2) the preparation method comprises the following steps: the preparation method can refer to the steps of preparing the polyester polyol in the preparation of the component A in the example, and the polyester polyol is prepared, wherein the hydroxyl value is 146, and the acid value is 0.9. Thus obtaining the component B.
Thirdly, the component A and the component B are mixed according to the mole ratio of functional groups-NCO: -OH ═ 1.54: 1.0 to form the adhesive. The adhesive is used for composite printing of PE40/PE40 (PE film after 40 micrometers), curing is carried out for 24 hours at 40 degrees, and the static friction coefficient and the dynamic friction coefficient are tested, wherein the test results are as follows: raw film, inner PE40 film inner PE40 film: the static friction coefficient is 0.17, and the dynamic friction coefficient is 0.15; the composite film printing PE40/PE40 has static friction coefficient of 0.18 and dynamic friction coefficient of 0.15. The friction coefficient is slightly increased due to different degrees of friction on the PE40 film in the compounding process. The static friction coefficient of the conventional solvent-free glue compounded with the designated printed PE40/PE40 film can be raised to 0.3-0.4.
Example two
The embodiment of the invention provides a solvent-free bi-component polyurethane adhesive, which consists of A, B components, wherein the A component is formed by the reaction of polyester polyol and polyisocyanate and is an addition product of modified isocyanate; the component B is polyester polyol which is modified polyol;
the A component and the B component can be prepared from the following components in a functional group molar ratio: -NCO: -OH ═ 1.75: 1.0 to form the adhesive.
The preparation method of the adhesive comprises the following steps:
firstly, preparing a component A:
preparing polyester polyol, comprising:
(1) preparing materials: 0.8mol of diethylene glycol, 0.2mol of ethylene glycol, 0.5mol of 1, 2-propanediol and 1.0mol of adipic acid;
(2) the preparation method comprises the following steps: reference may be made to the procedure for preparing the polyester polyol in the preparation of component a in example one;
preparing polyester polyol with a hydroxyl value of 128 and an acid value of 0.8;
(II) synthesizing a component A (the using amount of each component is in parts by weight):
(1) preparing materials: 39 parts of the above polyester polyol, 28 parts of MDI, 28 parts of blended MDI (2,4-MDI in 40%), 5 parts of PAPI;
(2) the preparation method comprises the following steps:
adding 28 parts of MDI, 28 parts of blended MDI (2,4-MDI accounts for 40 percent) and 5 parts of PAPI, keeping the kettle temperature at 25-35 ℃, adding 39 parts of polyester polyol, reacting for 3 hours at 75 ℃, and cooling to normal temperature to obtain the component A. Test a component NCO% ═ 16.52%.
Secondly, preparing a component B:
preparing a polyester polyol comprising:
(1) material preparation: 0.9mol of dipropylene glycol, 0.1mol of ethylene glycol, 0.1mol of 1, 4-butanediol, 0.1mol of 1, 2-propanediol, 0.4mol of 2-methyl-1, 3-propanediol, 0.55mol of adipic acid, 0.45mol of phthalic anhydride;
(2) the preparation method comprises the following steps: referring to the procedure for preparing polyester polyol in the preparation of component A in example one, polyester polyol was prepared and tested for hydroxyl value 158 and acid value 0.9. Thus obtaining the component B.
Thirdly, the component A and the component B are mixed according to the mole ratio of functional groups-NCO: -OH ═ 1.75: 1.0 to form the adhesive. The adhesive is used for composite printing of PE40/PE40 (PE film after 40 micrometers), curing is carried out for 24 hours at 40 degrees, and the static friction coefficient and the dynamic friction coefficient are tested, wherein the test results are as follows: raw film, inner PE40 film inner PE40 film: the static friction coefficient is 0.17, and the dynamic friction coefficient is 0.15; the composite film printing PE40/PE40 has the static friction coefficient of 0.19 and the dynamic friction coefficient of 0.17. The friction coefficient is slightly increased due to different degrees of friction on the PE40 film in the compounding process. The static friction coefficient of the conventional solvent-free glue compounded with the designated printed PE40/PE40 film can be raised to 0.3-0.4.
EXAMPLE III
The embodiment of the invention provides a solvent-free bi-component polyurethane adhesive, which consists of A, B components, wherein the A component is formed by the reaction of polyester polyol and polyisocyanate and is an addition product of modified isocyanate; the component B is polyester polyol which is modified polyol;
the A component and the B component can be prepared from the following components in a functional group molar ratio: -NCO: -OH ═ 1.4: 1.0 to form the adhesive.
Firstly, preparing a component A:
preparing polyester polyol, comprising:
(1) preparing materials: 0.25mol of diethylene glycol, 0.1mol of ethylene glycol, 0.7mol of 2-methyl-2, 4-pentanediol, 0.15mol of 1, 6-hexanediol, 0.6mol of adipic acid, 0.4mol of sebacic acid;
(2) the preparation method comprises the following steps: referring to the procedure for preparing the polyester polyol in the preparation of the component a in example one, the polyester polyol was prepared, and the hydroxyl value was measured to be 78, and the acid value was measured to be 0.3;
(II) synthesizing a component A (the using amount of each component is in parts by weight):
(1) preparing materials: 47 parts of the above polyester polyol, 20 parts of C-MDI, 30 parts of blended MDI (2,4-MDI ratio 40%), 3 parts of IPDI.
(2) The preparation method comprises the following steps:
adding 20 parts of C-MDI, 30 parts of blended MDI (the proportion of 2,4-MDI is 40 percent), 3 parts of IPDI, keeping the kettle temperature at 25-35 ℃, adding 47 parts of polyester polyol, reacting for 4 hours at 80 ℃, and cooling to normal temperature to obtain the component A. Test a component NCO% ═ 14.16%.
Secondly, preparing a component B:
preparing a polyester polyol comprising:
(1) preparing materials: 0.7mol of 1, 2-propanediol, 0.5mol of triethylene glycol, 0.2mol of 1, 4-cyclohexanedimethanol, 0.75mol of adipic acid and 0.25mol of isophthalic acid;
(2) the preparation method comprises the following steps: the preparation method can refer to the steps of preparing the polyester polyol in the component A of the example, and the polyester polyol is prepared, wherein the hydroxyl value is 109, and the acid value is 0.5. Thus obtaining the component B.
Thirdly, the component A and the component B are mixed according to the mole ratio of functional groups-NCO: -OH ═ 1.4: 1.0 to form the adhesive. The adhesive is used for composite printing of PE40/PE40 (PE film after 40 micrometers), curing is carried out for 24 hours at 40 degrees, and the static friction coefficient and the dynamic friction coefficient are tested, wherein the test results are as follows: raw film, inner PE40 film inner PE40 film: the static friction coefficient is 0.17, and the dynamic friction coefficient is 0.15; the composite film printing PE40/PE40 has static friction coefficient of 0.18 and dynamic friction coefficient of 0.16. The friction coefficient is slightly increased due to different degrees of friction on the PE40 film in the compounding process. The static friction coefficient of the common solvent-free glue compounded with the designated printing PE40/PE40 film can be increased to 0.3-0.4.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The solvent-free polyurethane adhesive with low friction coefficient is characterized by comprising a component A and a component B, wherein the molar ratio of functional groups of the component A to the component B is as follows: -NCO: -OH ═ 1.1 to 1.8: 1; wherein,
the component A adopts a modified isocyanate addition product formed by reacting modified polyester polyol with polyisocyanate;
the component B adopts modified polyester polyol.
2. The solvent-free polyurethane adhesive with a low coefficient of friction according to claim 1,
the mass percentage of NCO% of the component A is 8% -21%.
3. The solvent-free polyurethane adhesive with low friction coefficient as claimed in claim 1, wherein the polyester polyol in the component A and the polyester polyol in the component B are both synthesized by small molecular polyol and small molecular polybasic acid.
4. The solvent-free polyurethane adhesive with low friction coefficient as claimed in claim 3, wherein the polyester polyol in the A component and the B component is synthesized by a small molecular polyol and a small molecular polyacid in the following way:
the mol ratio of the small molecular polyol to the small molecular polyacid is as follows: -OH: -COOH ═ 1.2 to 1.8: 1.0, and obtaining the polyester polyol after reaction.
5. The solvent-free polyurethane adhesive with a low coefficient of friction according to claim 3 or 4,
the small molecular polyol adopted in the polyester polyol of the component A is selected from the following components: at least one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, 2-dimethyl-1, 3-propylene glycol, 1, 4-butanediol, 1, 2-pentanediol, 1, 5-pentanediol, 2-methyl-2, 4-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol;
the small molecular polyol adopted in the polyester polyol of the component B is selected from the following components: at least one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, 2-dimethyl-1, 3-propylene glycol, 1, 4-butanediol, 1, 2-pentanediol, 1, 5-pentanediol, 2-methyl-2, 4-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, glycerol, and trimethylolpropane.
6. The solvent-free polyurethane adhesive with a low coefficient of friction according to claim 5,
the polyester polyol of the component A at least comprises one of 1, 2-propylene glycol, 2-methyl-1, 3-propylene glycol, 2-dimethyl-1, 3-propylene glycol, 1, 2-pentanediol and 2-methyl-2, 4-pentanediol in small molecular polyol, and the using amount of the small molecular polyol accounts for 30-100% of the total mole number of the small molecular polyol;
the polyester polyol of the component B at least comprises one of 1, 2-propylene glycol, 2-methyl-1, 3-propylene glycol, 2-dimethyl-1, 3-propylene glycol, 1, 2-pentanediol, 2-methyl-2, 4-pentanediol, glycerol and trimethylolpropane in an amount of 30-100% of the total mole number of the small molecular polyol.
7. The solvent-free polyurethane adhesive with low friction coefficient as claimed in claim 6, wherein the polyester polyol of the component B further comprises at least one of glycerin and trimethylolpropane in the small molecular polyol, and the amount of the at least one of glycerin and trimethylolpropane is 0.1-5% of the total mole number of the small molecular polyol.
8. The solvent-free polyurethane adhesive with a low coefficient of friction according to claim 3 or 4,
the small molecular polybasic acid adopted in the polyester polyol of the component A is selected from the following groups: at least one of adipic acid and sebacic acid;
the small molecular polybasic acid adopted in the polyester polyol of the component B is selected from the following groups: at least one of adipic acid, sebacic acid, isophthalic acid, terephthalic acid, phthalic anhydride.
9. The low coefficient of friction solventless polyurethane adhesive of any one of claims 1 to 4 wherein the polyisocyanate in the A component is selected from the group consisting of:
a mixture of diphenylmethane-4, 4 '-diisocyanate, diphenylmethane-4, 4' -diisocyanate and diphenylmethane-2, 4 '-diisocyanate, wherein the weight ratio of 2, 4' isomer in the mixture is more than or equal to 25%, and at least one of polyether modified MDI, carbodiimide modified MDI, polymethylene polyphenyl polyisocyanate and isophorone diisocyanate;
the polyester polyol of the component B further comprises: and polycaprolactone diol or polycaprolactone triol accounting for 0.1-30% of the total weight of the component B.
10. A method for preparing a solvent-free polyurethane adhesive with a low coefficient of friction, characterized in that it is used for preparing the adhesive according to any one of claims 1 to 9, comprising the following steps:
preparing a modified polyester polyol of the component A and a modified polyester polyol of the component B respectively according to the formula of the adhesive of any one of claims 1 to 9;
preparing a component A: adding polyisocyanate, keeping the temperature of the kettle at 25-35 ℃, adding the prepared modified polyester polyol, reacting for 3-4 hours at 70-80 ℃, and cooling to normal temperature to obtain a component A;
the prepared component A and component B are prepared according to the molar ratio of functional groups as follows: -NCO: -OH ═ 1.1 to 1.8: 1, namely the solvent-free polyurethane adhesive is formed by matching.
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| CN110804158A (en) * | 2019-11-27 | 2020-02-18 | 南通高盟新材料有限公司 | Double-head coating solvent-free polyurethane adhesive and preparation method thereof |
| CN111423837A (en) * | 2020-04-08 | 2020-07-17 | 上海抚佳精细化工有限公司 | TPU hot melt adhesive and preparation method thereof |
| CN111621258A (en) * | 2020-06-05 | 2020-09-04 | 美邦（黄山）胶业有限公司 | Low-friction-coefficient bi-component solvent-free polyurethane adhesive |
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