CN111534265B - Ionic polyurethane hot melt adhesive foam product and preparation method thereof - Google Patents
Ionic polyurethane hot melt adhesive foam product and preparation method thereof Download PDFInfo
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- CN111534265B CN111534265B CN202010342936.8A CN202010342936A CN111534265B CN 111534265 B CN111534265 B CN 111534265B CN 202010342936 A CN202010342936 A CN 202010342936A CN 111534265 B CN111534265 B CN 111534265B
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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
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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
- C08G18/83—Chemically modified polymers
- C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
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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
- C08G18/83—Chemically modified polymers
- C08G18/833—Chemically modified polymers by nitrogen containing compounds
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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
- C08G18/83—Chemically modified polymers
- C08G18/836—Chemically modified polymers by phosphorus containing compounds
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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
- C09J175/06—Polyurethanes from polyesters
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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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Abstract
The invention belongs to the field of polymer high-molecular foaming materials, and particularly relates to an ionic polyurethane hot melt adhesive foam product and a preparation method thereof. The ionic polyurethane hot melt adhesive foam product comprises moisture curing polyurethane hot melt adhesive, ionic polyurethane hot melt adhesive and water. The preparation method comprises the following steps of carrying out graft reaction on an anionic surfactant containing active hydrogen and a polyurethane hot melt adhesive to prepare an ionic polymer containing NCO active groups, adding water at 35-95 ℃, and carrying out foaming reaction to prepare an ionic polyurethane foam product. Compared with the traditional polyurethane foam product, the ionic polyurethane hot melt adhesive foam product has the advantages that due to the grafting introduction of the anionic surfactant, after water is added, the hydrophilicity of a polymer system is increased, the ionic polyurethane hot melt adhesive foam product has a certain self-emulsifying effect, the foam stability is increased, the foam merging probability is reduced, foam holes are more compact and uniform, and the ionic polyurethane hot melt adhesive foam product has the characteristics of low compression deformation, high resilience, excellent mechanical strength and the like.
Description
Technical Field
The invention belongs to the field of polymer high-molecular foaming materials, and particularly relates to an ionic polyurethane hot melt adhesive foam product and a preparation method thereof.
Background
At present, most of foam plastics take plastics as a matrix, and a large amount of bubbles are obtained in the plastic matrix by adding a physical or chemical foaming agent. Foamed plastic materials have been widely used in the fields of daily necessities, shoe materials, sporting goods, packaging, construction, automobiles, and the like because of their light specific gravity and properties of heat insulation, shock absorption, sound absorption, and the like.
The prior art is superior in that NCO-reactive group-containing polymer is directly reacted with water to foam, so that the prepared polyurethane foam product has higher allophanate group content, and the allophanate group has higher polarity compared with the urethane group formed by the reaction of NCO group of the traditional polyurethane foam product and polymer polyol. Therefore, the polyurethane foam product prepared by the invention has the advantages of low compression deformation, high resilience, excellent mechanical strength and the like.
However, the unmodified organic high molecular polymer has very poor compatibility with water, thus causing cell breakage and uneven distribution of cells and cells in the polyurethane foam prepared by the method. Although part of technical schemes adopt a method of directly adding a surfactant as a foam stabilizer, the surfactant is micromolecule, so that the surfactant is easy to mix unevenly in a polymer system, and after water is added, micelles are easily formed and self-aggregation occurs, so that the mixing uniformity of the water and the polymer system cannot be improved well, and the foam uniformity degree of a final foaming product is not obviously improved. So that the technical problem of uneven foam of the foamed product is not solved.
Disclosure of Invention
The invention provides an ionic polyurethane hot melt adhesive foam product and a preparation method thereof, aiming at solving the technical problem of uneven foam of a foam product in the background technology.
The technical scheme adopted by the invention is as follows:
the invention provides an ionic polyurethane hot melt adhesive foam product which comprises, by weight, 100 parts of moisture-curing polyurethane hot melt adhesive, 1-10 parts of anionic surfactant and 1-10 parts of water, wherein: the moisture curing polyurethane hot melt adhesive comprises at least one polyisocyanate and at least one polymer polyol, wherein the molar ratio of NCO active groups in the polyisocyanate to hydroxyl groups in the polymer polyol is (1.5-2.5): 1.
the invention has the beneficial effects that: because moisture-curing polyurethane hot melt adhesives contain NCO-reactive groups. According to the invention, the anionic surfactant is grafted and modified on the moisture-cured polyurethane hot melt adhesive, so that the hydrophilicity of a polymer system is increased, the polyurethane hot melt adhesive is more uniformly mixed with water, the foam stability is increased, and the uniformity of a foam structure of a polyurethane foam product is obviously improved. The technical problem of uneven foam of a foaming product in the background technology is solved. Meanwhile, the physical properties of the polyurethane hot melt adhesive foam product, such as compression deformation, rebound resilience, mechanical strength and the like, can be further improved. In the process of generating carbon dioxide gas by reacting NCO active groups with water, because the polyurethane hot melt adhesive with an ionic structure is ionized when water exists, the hydrophilicity of the system is increased, the surface tension of a liquid-gas interface is reduced, the stability of bubbles is realized at the initial stage of bubble generation, the bubble merging probability is reduced, and the bubble holes are fine and smooth; when a large amount of NCO active groups react with water in the later period, the foam holes are fixed due to the formation of the allophanate crosslinking structure, so that the final foamed product has compact and uniform foam holes and a uniform structure. Meanwhile, compared with the urethane group formed by the reaction of NCO group of the traditional polyurethane foam product and polymer polyol, the allophanate has higher polarity and rigidity, so that the ionic polyurethane hot melt adhesive foam product has better mechanical property and better rebound resilience.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the polymer polyol is at least one of polyester polyol, polyether polyol and polyether ester polyol, and the content of polyether structure-containing polyol in the polymer polyol is 50 wt% or more.
The further scheme has the beneficial effect that the content of the polyether structure-containing polyol in the polyol ensures the reaction with the polyisocyanate. Better moisture curing polyurethane hot melt adhesive can be obtained.
Further, the number of carbon atoms contained in the structural unit of the polyether structure-containing polyol is 3 to 6.
The further scheme has the beneficial effects that the specific compound can be determined by the determined carbon number, so that better moisture curing polyurethane hot melt adhesive is obtained.
Further, the polymer polyol has a molar mass of 500 to 4000g/mol and a functionality of 1.8 to 2.2.
The beneficial effect of adopting the above further scheme is that better moisture curing polyurethane hot melt adhesive is obtained.
Further, the polyisocyanate is diphenylmethane-4, 4' -diisocyanate (MDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Xylylene Diisocyanate (XDI), hydrogenated xylylene diisocyanate (H6XDI) and hydrogenated diphenylmethane diisocyanate (H)12MDI).
The beneficial effect of adopting the further scheme is that the determined chemical combination reagent can obtain the ionic polyurethane hot melt adhesive foam product with better quality.
Further, the moisture curing polyurethane hot melt adhesive also contains 0.01-5 parts by weight of additive, wherein the additive is at least one of phosphoric acid, catalyst, antioxidant, light stabilizer, ultraviolet resistance auxiliary agent and mildew preventive.
The beneficial effect of adopting the further scheme is that the additive can play a better product promoting effect, improve the stability and the production speed and prolong the shelf life.
Further, the anionic surfactant contains active hydrogen capable of reacting with NCO active group, and the anionic surfactant contains at least one of sulfonate and phosphate.
The further scheme has the beneficial effects that active hydrogen on the anionic surfactant can more effectively react with NCO active groups, so that the reaction speed is increased, and the grafting modification is facilitated. Both sulfonates and phosphates are advantageous for graft modification.
Further, the sulfonate is one of sodium hydroxymethyl sulfonate, sodium hydroxyethyl sulfonate, sodium aminomethyl sulfonate, sodium aminoethyl sulfonate, sodium aminomethyl benzenesulfonate, sodium aminoethyl benzenesulfonate, sodium hydroxyethyl benzenesulfonate and sodium hydroxymethyl benzenesulfonate, and the phosphate is sodium aminotrimethylene phosphate.
The further scheme has the beneficial effects that the determined reagent can be more favorable for grafting modification, so that the ionic polyurethane hot melt adhesive foam product with high foam stability and uniform foam is obtained
Further, the content of NCO active groups in the ionic polyurethane hot melt adhesive foam product is 1-8%.
The beneficial effect of adopting the further scheme is that the quality of the obtained ionic polyurethane hot melt adhesive foam product is ensured by the content of NCO active groups.
The invention also provides a preparation method of the ionic polyurethane hot melt adhesive foam product, which comprises the following steps:
preparation of moisture-curing polyurethane hot melt adhesive
S1, adding polyester polyol, polyether polyol, phosphoric acid, an antioxidant, a light stabilizer, an ultraviolet-resistant auxiliary agent and a mildew preventive into a reaction kettle, melting, mixing and stirring at 120-130 ℃, and simultaneously vacuumizing and dehydrating for 1-2 hours under the condition that the vacuum degree is-0.09 MPa to-0.1 MPa to obtain a mixed material;
s2, cooling the mixed material obtained in the step S1 to 60-70 ℃, adding isocyanate, stirring, reacting at 60-70 ℃ under normal pressure for 10-15 min, heating to 100-110 ℃, vacuumizing, reacting for 1.5h under negative pressure, wherein the vacuum degree is-0.09 MPa to-0.1 MPa, and obtaining the moisture curing polyurethane hot melt adhesive;
preparation of ionic polyurethane hot melt adhesive
S3, keeping the moisture curing polyurethane hot melt adhesive obtained in the step S1 at the temperature of 110 ℃, adding an anionic surfactant, and reacting for 1h under the vacuum degree of-0.08 MPa to-0.1 MPa to obtain a reactant;
s4, adding a catalyst into the reactant of the step S3 at the temperature of 110 ℃, stirring, vacuumizing and defoaming until no bubbles appear, and discharging to obtain the ionic polyurethane hot melt adhesive containing NCO active groups;
preparation of ionic polyurethane hot melt adhesive foam product
S5, mixing the ionic polyurethane hot melt adhesive containing the NCO active group and water in the step S4 at 35-95 ℃ for 0.1-3min, and putting the mixture into a mold to react at 50-120 ℃ for 1-30 min to obtain the ionic polyurethane hot melt adhesive foam product.
The preparation method of the ionic polyurethane hot melt adhesive foam product has the beneficial effects of simplicity, easiness in operation, no environmental pollution, better economic feasibility and suitability for industrial production.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Examples 1,
A preparation method of an ionic polyurethane hot melt adhesive foam product comprises the following steps:
preparation of moisture-curing polyurethane hot melt adhesive
S1, adding 100g of polytetrahydrofuran polyether polyol with the molecular weight of 1800mol/L and the functionality of 2, 0.03g of phosphoric acid, 0.3g of antioxidant Irganox1010 (purchased from BASF company), 0.3g of light stabilizer Tinuvin 770 (purchased from BASF company), 0.5g of ultraviolet resistant auxiliary Tinuvin327 (purchased from BASF company) and 0.5g of mildew preventive AM110 (purchased from Hensman company) into a reaction kettle, melting, mixing and stirring at 120 ℃, and vacuumizing and dehydrating for 2 hours under the condition that the vacuum degree is-0.09 MPa to obtain a mixed material;
s2, cooling the mixed material obtained in the step S1 to 60 ℃, adding 27.8g of diphenylmethane-4, 4' -diisocyanate (MDI) to stir, reacting at 60 ℃ under normal pressure for 15min, heating to 110 ℃, vacuumizing and reacting under negative pressure for 1.5h, wherein the vacuum degree is-0.09 MPa, and thus obtaining the moisture-cured polyurethane hot melt adhesive containing NCO active groups;
preparation of ionic polyurethane hot melt adhesive
S3, keeping the moisture curing polyurethane hot melt adhesive obtained in the step S2 at the temperature of 110 ℃, adding 5g of anionic surfactant sodium hydroxymethyl sulfonate, and reacting for 1h under the vacuum degree of-0.08 MPa to obtain a reactant;
s4, adding 0.3g of dimorpholinyl diethyl ether catalyst into the reactant of the step S3 at the temperature of 110 ℃, stirring, vacuumizing and defoaming until no bubbles appear, and discharging to obtain the ionic polyurethane hot melt adhesive containing NCO active groups; the technical indexes of the product are tested as shown in the table 1.
Preparation of ionic polyurethane hot melt adhesive foam product
S5, taking 100g of the ionic polyurethane hot melt adhesive containing the NCO active group in the step S4 and 5g of water, mixing for 2min at 50 ℃, putting into a mold, reacting for 30min at 90 ℃, applying pressure of 0.1Mpa to the mold, cooling the mold to 20 ℃, and opening the mold to obtain the ionic polyurethane hot melt adhesive foam product. The technical indexes of the obtained ionic polyurethane hot melt adhesive foam product are shown in the table 1.
Examples 2,
A preparation method of an ionic polyurethane hot melt adhesive foam product comprises the following steps:
preparation of moisture-curing polyurethane hot melt adhesive
S1, adding 60g of polytetrahydrofuran polyol with the molecular weight of 2000mol/L and the functionality of 2, 40g of polybutanediol adipate with the molecular weight of 2000mol/L and the functionality of 2, 0.03g of phosphoric acid, 0.3g of antioxidant Irganox1010 (obtained from BASF company), 0.3g of light stabilizer Tinuvin 770 (obtained from BASF company), 0.5g of ultraviolet-resistant auxiliary Tinuvin327 (obtained from BASF company) and 0.5g of mildew preventive AM110 (obtained from Hensman company) into a reaction kettle, melting, mixing and stirring at 120 ℃, and vacuumizing and dehydrating for 2 hours under the condition that the vacuum degree is-0.09 MPa to obtain a mixed material;
s2, cooling the mixed material obtained in the step S1 to 60 ℃, adding 22g of diphenylmethane-4, 4' -diisocyanate (MDI) to stir, reacting at 60 ℃ for 15min under normal pressure, heating to 110 ℃, vacuumizing and reacting under negative pressure for 1.5h, wherein the vacuum degree is-0.09 MPa, so as to obtain the moisture curing polyurethane hot melt adhesive containing NCO active groups;
preparation of ionic polyurethane hot melt adhesive
S3, keeping the moisture curing polyurethane hot melt adhesive obtained in the step S1 at the temperature of 110 ℃, adding 8g of anionic surfactant sodium hydroxyethyl sulfonate, and reacting for 1h under the vacuum degree of-0.08 MPa to obtain a reactant;
s4, adding 0.3g of dimorpholinyl diethyl ether catalyst into the reactant of the step S3 at the temperature of 110 ℃, stirring, vacuumizing and defoaming until no bubbles appear, and discharging to obtain the ionic polyurethane hot melt adhesive containing NCO active groups; the technical indexes of the product are tested as shown in the table 1.
Preparation of ionic polyurethane hot melt adhesive foam product
S5, taking 100g of the NCO active group-containing ionic polyurethane hot melt adhesive in the step S4 and 3g of water, mixing for 2min at 50 ℃, putting into a mold, reacting for 30min at 90 ℃, applying pressure of 0.1Mpa to the mold, cooling the mold to 20 ℃, and opening the mold to obtain the ionic polyurethane hot melt adhesive foam product. The technical indexes of the obtained ionic polyurethane hot melt adhesive foam product are shown in the table 1.
Examples 3,
A preparation method of an ionic polyurethane hot melt adhesive foam product comprises the following steps:
preparation of moisture-curing polyurethane hot melt adhesive
S1, 100g of polytetrahydrofuran polyol with the molecular weight of 1000mol/L and the functionality of 2, 0.03g of phosphoric acid, 0.3g of antioxidant Irganox1010 (purchased from BASF company), 0.3g of light stabilizer Tinuvin 770 (purchased from BASF company), 0.5g of ultraviolet resistant auxiliary Tinuvin327 (purchased from BASF company) and 0.5g of mildew preventive AM110 (purchased from Hensman company) are added into a reaction kettle, and the mixture is obtained after melt mixing and stirring at the temperature of 120 ℃ and vacuum pumping and dehydration for 2 hours under the condition that the vacuum degree is-0.09 MPa;
s2, cooling the mixed material obtained in the step S1 to 60 ℃, adding 45g of diphenylmethane-4, 4' -diisocyanate (MDI) to stir, reacting at 60 ℃ for 15min under normal pressure, heating to 110 ℃, and performing vacuum pumping negative pressure reaction for 1.5h at the vacuum degree of-0.09 MPa to obtain the moisture curing polyurethane hot melt adhesive;
preparation of ionic polyurethane hot melt adhesive
S3, keeping the moisture curing polyurethane hot melt adhesive obtained in the step S1 at the temperature of 110 ℃, adding 2g of an anionic surfactant sodium aminomethyl sulfonate, and reacting for 1h under the vacuum degree of-0.08 MPa to obtain a reactant;
s4, adding 0.3g of dimorpholinyl diethyl ether catalyst into the reactant of the step S3 at the temperature of 110 ℃, stirring, vacuumizing and defoaming until no bubbles appear, and discharging to obtain the ionic polyurethane hot melt adhesive containing NCO active groups; the technical indexes of the product are tested as shown in the table 1.
Preparation of ionic polyurethane hot melt adhesive foam product
S5, taking 100g of the ionic polyurethane hot melt adhesive containing the NCO active group in the step S4 and 10g of water, mixing for 2min at 50 ℃, putting into a mold, reacting for 30min at 90 ℃, applying pressure of 0.1Mpa to the mold, cooling the mold to 20 ℃, and opening the mold to obtain the ionic polyurethane hot melt adhesive foam product. The technical indexes of the obtained ionic polyurethane hot melt adhesive foam product are shown in the table 1.
Examples 4,
A preparation method of an ionic polyurethane hot melt adhesive foam product comprises the following steps:
preparation of moisture-curing polyurethane hot melt adhesive
S1, adding 100g of polytetrahydrofuran polyol with the molecular weight of 2400mol/L and the functionality of 2, 0.03g of phosphoric acid, 0.3g of antioxidant Irganox1010 (purchased from BASF company), 0.3g of light stabilizer Tinuvin 770 (purchased from BASF company), 0.5g of ultraviolet resistant auxiliary Tinuvin327 (purchased from BASF company) and 0.5g of mildew preventive AM110 (purchased from Hensman company) into a reaction kettle, melting, mixing and stirring at 120 ℃, and vacuumizing and dehydrating for 2 hours under the condition that the vacuum degree is-0.09 MPa to obtain a mixed material;
s2, cooling the mixed material obtained in the step S1 to 60 ℃, adding 22.9g of diphenylmethane-4, 4' -diisocyanate (MDI) to stir, reacting at 60 ℃ under normal pressure for 15min, heating to 110 ℃, and carrying out vacuum pumping and negative pressure reaction for 1.5h with the vacuum degree of-0.09 MPa to obtain the moisture curing polyurethane hot melt adhesive;
preparation of ionic polyurethane hot melt adhesive
S3, keeping the moisture curing polyurethane hot melt adhesive obtained in the step S1 at the temperature of 110 ℃, adding 3g of anionic surfactant aminomethyl sodium benzenesulfonate, and reacting for 1h under the vacuum degree of-0.08 MPa to obtain a reactant;
s4, adding 0.3g of dimorpholinyl diethyl ether catalyst into the reactant of the step S3 at the temperature of 110 ℃, stirring, vacuumizing and defoaming until no bubbles appear, and discharging to obtain the ionic polyurethane hot melt adhesive containing NCO active groups; the technical indexes of the product are tested as shown in the table 1.
Preparation of ionic polyurethane hot melt adhesive foam product
S5, taking 100g of the NCO active group-containing ionic polyurethane hot melt adhesive in the step S4 and 3g of water, mixing for 2min at 50 ℃, putting into a mold, reacting for 30min at 90 ℃, applying pressure of 0.1Mpa to the mold, cooling the mold to 20 ℃, and opening the mold to obtain the ionic polyurethane hot melt adhesive foam product. The technical indexes of the obtained ionic polyurethane hot melt adhesive foam product are shown in the table 1.
Examples 5,
A preparation method of an ionic polyurethane hot melt adhesive foam product comprises the following steps:
preparation of moisture-curing polyurethane hot melt adhesive
S1, adding 100g of polycaprolactone-polytetrahydrofuran polyol block polymer with the molecular weight of 1000mol/L and the functionality of 2, 0.03g of phosphoric acid, 0.3g of antioxidant Irganox1010 (purchased from BASF company), 0.3g of light stabilizer Tinuvin 770 (purchased from BASF company), 0.5g of ultraviolet resistant auxiliary Tinuvin327 (purchased from BASF company) and 0.5g of mildew preventive AM110 (purchased from Hensman company) into a reaction kettle, melting, mixing and stirring at 120 ℃, and vacuumizing and dehydrating for 2 hours under the condition that the vacuum degree is-0.09 MPa to obtain a mixed material;
s2, cooling the mixed material obtained in the step S1 to 60 ℃, adding 50g of diphenylmethane-4, 4' -diisocyanate (MDI) to stir, reacting at 60 ℃ for 15min under normal pressure, heating to 110 ℃, and performing vacuum pumping negative pressure reaction for 1.5h at the vacuum degree of-0.09 MPa to obtain the moisture curing polyurethane hot melt adhesive;
preparation of ionic polyurethane hot melt adhesive
S3, keeping the moisture curing polyurethane hot melt adhesive obtained in the step S1 at the temperature of 110 ℃, adding 9g of anionic surfactant aminoethyl benzene sulfonate, and reacting for 1h under the vacuum degree of-0.08 MPa to obtain a reactant;
s4, adding 0.3g of dimorpholinyl diethyl ether catalyst into the reactant of the step S3 at the temperature of 110 ℃, stirring, vacuumizing and defoaming until no bubbles appear, and discharging to obtain the ionic polyurethane hot melt adhesive containing NCO active groups; the technical indexes of the product are tested as shown in the table 1.
Preparation of ionic polyurethane hot melt adhesive foam product
S5, taking 100g of the NCO active group-containing ionic polyurethane hot melt adhesive in the step S4 and 6g of water, mixing for 2min at 50 ℃, putting into a mold, reacting for 30min at 90 ℃, applying pressure of 0.1Mpa to the mold, cooling the mold to 20 ℃, and opening the mold to obtain the ionic polyurethane hot melt adhesive foam product. The technical indexes of the obtained ionic polyurethane hot melt adhesive foam product are shown in the table 1.
Examples 6,
A preparation method of an ionic polyurethane hot melt adhesive foam product comprises the following steps:
preparation of moisture-curing polyurethane hot melt adhesive
S1, adding 50g of polytetrahydrofuran polyether polyol with the molecular weight of 1800mol/L and the functionality of 2, 50g of neopentyl glycol adipate with the molecular weight of 1000mol/L and the functionality of 2, 0.03g of phosphoric acid, 0.3g of antioxidant Irganox1010 (obtained from BASF company), 0.3g of light stabilizer Tinuvin 770 (obtained from BASF company), 0.5g of ultraviolet-resistant auxiliary Tinuvin327 (obtained from BASF company) and 0.5g of mildew preventive AM110 (obtained from Hensman company) into a reaction kettle, melting, mixing and stirring at 120 ℃, and vacuumizing and dehydrating for 2 hours under the condition that the vacuum degree is-0.09 MPa to obtain a mixed material;
s2, cooling the mixed material obtained in the step S1 to 60 ℃, adding 29g of diphenylmethane-4, 4' -diisocyanate (MDI) to stir, reacting at 60 ℃ for 15min under normal pressure, heating to 110 ℃, and performing vacuum pumping negative pressure reaction for 1.5h at the vacuum degree of-0.09 MPa to obtain the moisture curing polyurethane hot melt adhesive;
preparation of ionic polyurethane hot melt adhesive
S3, keeping the moisture curing polyurethane hot melt adhesive obtained in the step S1 at the temperature of 110 ℃, adding 13g of anionic surfactant sodium hydroxyethyl benzene sulfonate, and reacting for 1h under the vacuum degree of-0.08 MPa to obtain a reactant;
s4, adding 0.3g of dimorpholinyl diethyl ether catalyst into the reactant of the step S3 at the temperature of 110 ℃, stirring, vacuumizing and defoaming until no bubbles appear, and discharging to obtain the ionic polyurethane hot melt adhesive containing NCO active groups; the technical indexes of the product are tested as shown in the table 1.
Preparation of ionic polyurethane hot melt adhesive foam product
S5, taking 100g of the NCO active group-containing ionic polyurethane hot melt adhesive in the step S4 and 8g of water, mixing for 2min at 50 ℃, putting into a mold, reacting for 30min at 90 ℃, applying pressure of 0.1Mpa to the mold, cooling the mold to 20 ℃, and opening the mold to obtain the ionic polyurethane hot melt adhesive foam product. The technical indexes of the obtained ionic polyurethane hot melt adhesive foam product are shown in the table 1.
Comparative examples 1,
A preparation method of a polyurethane hot melt adhesive foam product is different from that of the embodiment 1 in that the preparation step of ionic polyurethane hot melt adhesive in the step two is omitted, and 100g of moisture-cured polyurethane hot melt adhesive containing NCO active groups prepared in the step one is taken in the step three and mixed with 5g of water to obtain the polyurethane hot melt adhesive foam product. The technical indexes of the obtained polyurethane hot melt adhesive foam product are shown in the table 1.
Comparative examples 2,
A preparation method of a polyurethane hot melt adhesive foam product is different from that of embodiment 1 in that a preparation step of an ionic polyurethane hot melt adhesive in a step two is omitted, 100g of moisture-cured polyurethane hot melt adhesive containing NCO active groups prepared in the step one, 3.9g of anionic surfactant sodium hydroxymethanesulfonate and 5.2g of water are taken in a step three, after the moisture-cured polyurethane hot melt adhesive, the anionic surfactant sodium hydroxymethanesulfonate and the water are uniformly mixed by hand, the mixing temperature is controlled to be 50 ℃, the mixing time is 2 minutes, then the mixture is put into a mold at 90 ℃, the pressure of 0.1Mpa is applied to the mold, the mixture is kept for 30 minutes, the mold is cooled to 20 ℃, and the mold is opened, so that the polyurethane hot melt adhesive foam product is obtained. The technical indexes of the obtained polyurethane hot melt adhesive foam product are shown in the table 1.
Test for measuring Effect
The polyurethane foam products prepared in examples 1-6 and comparative examples 1 and 2 were all placed in an environment of 25 ℃ and 60% relative humidity, and after 24 hours of storage, the tests of various performance technical indexes were performed.
(1) The viscosities of the ionic polyurethane hot melt adhesive and the polyurethane hot melt adhesive are obtained by adopting a Nihon NTV-Al250 viscometer to test at the temperature of 50 ℃;
(2) the cell size of the foamed polyurethane hot melt adhesive sheet (i.e. the ionic polyurethane hot melt adhesive foam product/polyurethane hot melt adhesive foam product) is the range of the major diameter size of 100 cells by observing the cells of the section of the sheet through an electron microscope;
(3) compression deformation: cutting the foam into 2.5cm × 2.5cm × 1cm blocks, recording the initial thickness d0 as 1cm, placing in a mold for compression by 50%, placing at 50 deg.C for 6h, taking out, placing at room temperature for 30min, measuring the thickness as d1, and calculating the compression deformation as (d0-d1)/d 0;
(4) linear shrinkage ratio: the longest dimension of the foam article is measured and compared to the longest dimension of the mold, and the linear shrinkage is reported as the percent reduction from the longest dimension of the mold.
The results obtained are shown in table 1 below:
table 1 test data for ionic polyurethane hot melt adhesive and ionic polyurethane hot melt adhesive foam products
As can be seen from the data in Table 1, compared with the moisture-curing polyurethane hot melt adhesive containing NCO active groups which is directly foamed by adding water, and the moisture-curing polyurethane hot melt adhesive containing NCO active groups which is mixed with anionic surfactant and water for foaming, the invention firstly carries out the grafting modification of the anionic surfactant on the moisture-curing polyurethane hot melt adhesive containing NCO active groups to prepare the ionic polyurethane hot melt adhesive, and then carries out the foaming, the obtained foam product has the obvious advantages of narrow cell size distribution, more uniform structure, higher closed cell rate, lower compression deformation, more excellent mechanical strength and higher rebound resilience, the foaming ionic polyurethane hot melt adhesive sheet has wide application prospect in the fields of soles, insoles, vamps, bicycle seats, interior ornaments, buffer pads, sound insulation pads, children toys, ground coverings and the like.
In the description herein, the description of the terms "one embodiment," "some embodiments," "specific embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. The ionic polyurethane hot melt adhesive foam product is characterized by comprising 100 parts by weight of moisture curing polyurethane hot melt adhesive, 1-10 parts by weight of anionic surfactant and 1-10 parts by weight of water, wherein:
the preparation method of the ionic polyurethane hot melt adhesive foam product comprises the following steps:
preparation of moisture-curing polyurethane hot melt adhesive
S1, melting, mixing and stirring polyester polyol, polyether polyol, phosphoric acid, an antioxidant, a light stabilizer, an ultraviolet-resistant auxiliary agent and a mildew preventive at 120-130 ℃, and simultaneously vacuumizing and dehydrating for 1-2 hours under the condition that the vacuum degree is-0.09 MPa to-0.1 MPa to obtain a mixed material;
s2, cooling the mixed material obtained in the step S1 to 60-70 ℃, adding polyisocyanate, stirring, reacting at 60-70 ℃ under normal pressure for 10-15 min, heating to 100-110 ℃, vacuumizing, reacting for 1.5h under negative pressure, and obtaining the moisture curing polyurethane hot melt adhesive, wherein the vacuum degree is-0.09 MPa to-0.1 MPa; the molar ratio of NCO active groups in the polyisocyanate to hydroxyl groups in the polyester polyol and the polyether polyol is (1.5-2.5): 1;
preparation of ionic polyurethane hot melt adhesive
S3, keeping the moisture curing polyurethane hot melt adhesive obtained in the step S2 at the temperature of 110 ℃, adding an anionic surfactant, and reacting for 1h under the vacuum degree of-0.08 MPa to-0.1 MPa to obtain a reactant;
s4, adding a catalyst into the reactant of the step S3 at the temperature of 110 ℃, stirring, vacuumizing and defoaming until no bubbles appear, and discharging to obtain the ionic polyurethane hot melt adhesive containing NCO active groups; the anionic surfactant contains active hydrogen capable of reacting with NCO active groups, and the anionic surfactant contains at least one of sulfonate and phosphate;
preparation of ionic polyurethane hot melt adhesive foam product
S5, mixing the ionic polyurethane hot melt adhesive containing the NCO active group and water in the step S4 at 35-95 ℃ for 0.1-3min, and putting the mixture into a mold to react at 50-120 ℃ for 1-30 min to obtain the ionic polyurethane hot melt adhesive foam product.
2. The ionic polyurethane hot melt adhesive foam product of claim 1, wherein the number of carbon atoms contained in each structural unit of the polyether polyol is 3 to 6.
3. The ionic polyurethane hot melt adhesive foam product of claim 1, wherein the polyester polyol and the polyether polyol are both 500 to 4000g/mol in molar mass and 1.8 to 2.2 in functionality.
4. The ionic polyurethane hot melt adhesive foam article of claim 1, wherein the polyisocyanate is at least one of diphenylmethane-4, 4' -diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.
5. The ionic polyurethane hot melt adhesive foam article of claim 1, wherein said sulfonate is one of sodium hydroxymethylsulfonate, sodium isethionate, sodium aminomethylsulfonate, sodium aminoethyl sulfonate, sodium aminomethylbenzenesulfonate, sodium aminoethylbenzene sulfonate, sodium hydroxyethylbenzenesulfonate and sodium hydroxymethylbenzenesulfonate, and said phosphate is sodium aminotrimethylene phosphate.
6. The ionic polyurethane hot melt adhesive foam product according to any one of claims 1 to 5, wherein the content of NCO active groups in the ionic polyurethane hot melt adhesive foam product is 1-8%.
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| CN103030765A (en) * | 2012-12-10 | 2013-04-10 | 中国科学院福建物质结构研究所 | Sulfonate-terminated hyperbranched water-based polyurethane emulsion and preparation method thereof |
| CN106750086A (en) * | 2016-12-14 | 2017-05-31 | 浙江吉高新材料有限公司 | A kind of high-performance reaction injection molding polyurethane and preparation method thereof |
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| US3988268A (en) * | 1972-02-17 | 1976-10-26 | Bayer Aktiengesellschaft | Polyurethane foam plastics which contain ionic groups |
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| US20140171525A1 (en) * | 2011-02-21 | 2014-06-19 | Honeywell International Inc. | Polyurethane foam premixes containing halogenated olefin blowing agents and foams made from same |
| DE102011079791A1 (en) * | 2011-07-26 | 2013-01-31 | Evonik Goldschmidt Gmbh | Additive composition, which can be used to control the foam properties in the production of flexible polyurethane foams containing polyols based on renewable raw materials |
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| JP6186033B1 (en) * | 2016-03-31 | 2017-08-23 | 株式会社ジェイエスピー | Thermoplastic polyurethane foam particles and method for producing thermoplastic polyurethane foam particles |
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| DE102018215651A1 (en) * | 2018-09-14 | 2020-03-19 | Tesa Se | Elastic flame-retardant polyurethane foam, adhesive tape with a carrier made of it and manufacturing process therefor |
| CN110066417B (en) * | 2019-04-26 | 2021-07-20 | 濮阳绿宇新材料科技股份有限公司 | Preparation method of amino particle cotton |
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| CN106750086A (en) * | 2016-12-14 | 2017-05-31 | 浙江吉高新材料有限公司 | A kind of high-performance reaction injection molding polyurethane and preparation method thereof |
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