CN111607352A - Light, heat and moisture cured PUR hot melt adhesive for textiles and preparation method thereof - Google Patents
Light, heat and moisture cured PUR hot melt adhesive for textiles and preparation method thereof Download PDFInfo
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- CN111607352A CN111607352A CN202010527334.XA CN202010527334A CN111607352A CN 111607352 A CN111607352 A CN 111607352A CN 202010527334 A CN202010527334 A CN 202010527334A CN 111607352 A CN111607352 A CN 111607352A
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- 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
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- 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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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- 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
- C08G18/4829—Polyethers containing at least three hydroxy groups
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- 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
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
Abstract
The invention provides a light, heat and moisture cured PUR hot melt adhesive for textiles and a preparation method thereof, wherein the light, heat and moisture cured PUR hot melt adhesive for textiles comprises diisocyanate, hydroxyl acrylate, polyether polyol, polyester polyol, a chain extender, a latent curing agent, phosphoric acid, a photoinitiator, an antioxidant, a light stabilizer and an ultraviolet absorber. The preparation method of the PUR hot melt adhesive comprises the steps of raw material dehydration, monomer mixing, reaction with acrylate, prepolymer reaction, prepolymer chain extension, addition of an auxiliary agent and addition of a latent curing agent. The light, heat and moisture cured PUR hot melt adhesive for textiles has the advantages of high curing rate, long storage time and no pollution in the preparation process; and anti-yellowing raw materials such as HMDI, IPDI, HDI, polyether and polyester are adopted, so that the anti-yellowing performance of the fabric is effectively improved, the fabric is particularly suitable for colorful and light-colored textiles, the color of the textile is bright, and the market competitiveness is improved.
Description
Technical Field
The invention relates to the technical field of hot melt adhesive, in particular to a light, heat and moisture curing PUR hot melt adhesive for textile and a preparation method thereof.
Background
With the rapid development of modern science and technology, the adhesive industry is accompanied with rapid growth along with the development of modern industry. In order to protect the environment and prevent pollution, the state develops low-pollution or zero-pollution environment-friendly adhesives by many policies. Is the major responsibility of current science and technical personnel. The adhesive is nontoxic to human bodies and meets the requirements of environmental protection, health and safety. The aqueous adhesive is environment-friendly to the adhesive itself, but the purification of waste water is troublesome. Reactive hot melt adhesives (PURHM) are those which are currently generally regarded as excellent in performance.
Compared with the hot melt adhesive, the condensation performance of the cured PUR is higher than that of the hot melt adhesive, and because isocyanate and water react, allophanate is generated, and the tensile strength is improved;
the PUR of the textile adhesive has higher requirement on the content of-NCO, and needs to be controlled between 3 percent and 5 percent; when-NCO is less than 3%, the viscosity of the spinning glue is too high, the use temperature of the spinning glue is not too high, otherwise the coating is not uniform, and the influence on a thin substrate is larger particularly; when the content of-NCO is more than 5%, a hot melt adhesive cannot be formed, and preparation failure is caused.
In the prior art, the content of the-NCO in the PUR hot melt adhesive is difficult to control, and the prepared PUR has longer curing time and poor storage stability; in addition, it gives off CO during the reaction2The product is easy to form bubbles and has poor yellowing resistance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the PUR hot melt adhesive for spinning, which is environment-friendly, yellowing-resistant, high in curing rate and good in storage property, and the preparation method thereof
In order to achieve the purpose, the invention adopts the following technical scheme:
a light, heat, moisture curable PUR hot melt adhesive for textile use according to an embodiment of the first aspect of the invention comprises the following components:
57-74 parts of diisocyanate;
12-17 parts of hydroxyl acrylate;
77-117 parts of polyether polyol;
3.5-7 parts of polyester polyol;
2.5-5 parts of a chain extender;
8-12 parts of a latent curing agent;
0.01-0.014 part of phosphoric acid;
0.15-0.35 part of photoinitiator;
0.15-0.25 part of antioxidant;
0.1-0.2 part of light stabilizer;
0-0.3 part of ultraviolet absorbent.
Further, the diisocyanate comprises aromatic and/or aliphatic, the aromatic diisocyanate comprises MDI-100 and MDI-50, and the aliphatic diisocyanate comprises IPDI, HDI and HMDI;
MDI is an important raw material for preparing the PUR hot melt adhesive, and has good mechanical property, high reaction activity, small volatility, small damage to people and low cost;
HMDI is a hydrogenated MDI, which is excellent in resistance to yellowing, and is commonly used in fabric coatings and radiation curable polyurethane-acrylic coatings; its structure is similar to MDI, thus inheriting many of the excellent properties of MDI: excellent mechanical property, better reaction activity, excellent weather resistance, good light-resistant stability, excellent hydrolysis resistance and excellent chemical property;
IPDI has yellowing resistance and excellent light stability, chemical drug resistance, wear resistance and hydrolysis resistance; the HDI has excellent yellowing resistance and excellent flexibility;
and the diisocyanate is a mixture consisting of more than two of MDI-100, MDI-50, HMDI, HDI and IPDI, so that the PUR hot melt adhesive with excellent comprehensive performance is obtained.
Further, the hydroxy acrylic monomer is beta-hydroxyethyl acrylate or beta-hydroxypropyl acrylate or hydroxyethyl methacrylate or hydroxypropyl methacrylate.
Further, the polyether polyol is a mixture of polyether diol and polyether triol, the polyether diol is a mixture of at least two of PTMEG1000, polyether 2070 and polyether 210, and the polyether triol is polyether 3010;
the 3-functionality polyether polyol is used for improving the crosslinking density of the adhesive, the 2-functionality polyether polyol is used for adjusting the viscosity of the adhesive, and the 3-functionality polyether polyol and the 2-functionality polyether polyol are used in a matched mode to balance the crosslinking density and viscosity of the adhesive and enable the adhesive to reach the optimal state.
Further, the polyester polyol is polyester PHN-56 or polyester Priplast 3192; the polyester PHN-56 is polyester dihydric alcohol prepared from dihydric alcohol with even number of carbon atoms, has higher crystallinity, and is beneficial to improving the initial strength of the PUR hot melt adhesive; the polyester PrIPlast3192 is polyester diol prepared from dihydric alcohol with a side chain, and has good flexibility and water resistance.
Further, the chain extender is 1, 4-butanediol or trimethylolpropane or diethylene glycol, and is used for improving the firmness, corrosion resistance, hydrolysis resistance, thermal decomposition resistance and oxidation resistance of the adhesive.
Further, the latent curing agent is a CH type curing agent which is divided into CH-4, CH-3 and CH-2; the CH type curing agent is different from other latent curing agents, has the advantages of environmental protection, no toxicity and no odor, and is an environment-friendly latent curing agent;
taking CH-3 as an example, the reaction speed of the compound with water is far higher than that of-NCO and water, when the compound meets moisture in air, CH-3 can quickly react with water to generate a compound with an active hydrogen group of two functional groups, and the active hydrogen compound is reacted with-NCO in the prepolymer of the systemChemical reaction, which makes the chain of polyurethane prepolymer be extended continuously and prevents-NCO group from reacting with water, thus preventing CO2The generation of bubbles is avoided;
meanwhile, the CH-type curing agent has the advantages that the speed of generating active H is increased, the curing speed of the adhesive is increased, and the catalytic effect is achieved; the CH-type curing agent can effectively solve the foaming problem caused in the curing process, adjust the curing speed, and enable the adhesive to have good storage stability, safety and environmental protection; the application of the CH-type curing agent to the PUR of the textile adhesive is not found at present;
and/or the photoinitiator is photoinitiator 819 or photoinitiator 379 or photoinitiator 184;
the photoinitiator 819 is phenyl bis (2, 4, 6-trimethyl benzoyl) phosphine oxide with the molecular weight of 418.16 and the melting point of 127-131 ℃, has great absorption in an ultraviolet region and a visible region, can be printed and cured more effectively than other photoinitiators, and hardly generates yellowing under the condition of long-term light radiation;
the photoinitiator 379 is 2-dimethylamino-2- (4-methyl) benzyl-1 [4- (4-morpholinyl) phenyl ] -1-butanone, has the molecular weight of 380.5, the melting point of 82-87 ℃, belongs to alpha-aminoketone derivatives, and has the advantages of good thermal stability, long storage period, good solubility, light color, good yellowing resistance, high photocuring speed and good deep curing performance;
the photoinitiator 184 is 1-hydroxycyclohexyl phenyl ketone, has the molecular weight of 204.3 and the melting point of 45-49 ℃, is a high-efficiency free radical I type non-yellowing photoinitiator, and is used in common adhesives;
and/or the antioxidant is antioxidant PUR68 or antioxidant 245 or antioxidant 1010, and the antioxidant is used for preventing polyurethane from thermal-oxidative degradation and influencing the performance of the adhesive;
the antioxidant PUR68 is a novel heat stabilizer mixture, has excellent smog resistance and textile stain resistance, and has the effect of inhibiting yellowing; the antioxidant 245 has low toxicity, is a sterically hindered phenolic antioxidant, prevents the material from being degraded by heating, is tasteless, and has good color stability; the antioxidant 1010 is a high molecular weight hindered phenol antioxidant, and can effectively prevent the thermal aging degradation of the polymer material in a long-term aging process;
and/or the light stabilizer is light stabilizer 692 or light stabilizer 765, the light stabilizer 692 is a new generation polymer high molecular hindered amine light stabilizer; the light stabilizer 765 is a hindered amine light stabilizer which is used in combination with an ultraviolet absorber to obtain a good synergistic effect for obtaining an optimal light stabilization effect, and an antioxidant is added to the polymer;
and/or the ultraviolet absorber is UV-327 or UV-328;
UV-327 is a hydroxybenzotriazole high-efficiency ultraviolet absorbent which can strongly absorb ultraviolet with the wavelength of 300-400nm, absorbs little in the visible light region (the wavelength is more than 400 nm), and is particularly suitable for the ultraviolet radiation with long wavelength;
the ultraviolet absorbent UV-328 is a high-efficiency ultraviolet absorbent, and can effectively absorb ultraviolet rays with the wavelength of 270-380 nm.
Further, the adhesive comprises the following components in parts by weight:
30-34 parts of HMDI;
20-30 parts of IPDI;
7-10 parts of HDI;
12-17 parts of hydroxypropyl methacrylate;
301030-50 parts of polyether;
PTMEG 100040-50 shares;
207012-17 parts of polyether;
polyester Priplast 31925-7 parts;
3-5 parts of trimethylolpropane;
CH-48-12 parts;
0.010-0.014 portion of phosphoric acid;
3790.15-0.25 part of photoinitiator;
10100.15-0.25 part of antioxidant;
7650.1-0.2 part of light stabilizer;
0.3 part of ultraviolet absorbent UV-3280.15;
the HMDI accounts for 50% of the total amount of the HMDI, the IPDI and the HDI, the HMDI, the IPDI and the HDI are compounded to form a mixed diisocyanate mixture, the HMDI, the IPDI and the HDI have excellent yellowing resistance, and the yellowing resistance of the PUR hot melt adhesive prepared from the HMDI, the IPDI and the HDI is effectively improved.
Further, the adhesive comprises the following components in parts by weight:
MDI-10023-28 parts;
MDI-5023-28 parts;
12-15 parts of IPDI;
12-17 parts of hydroxypropyl methacrylate;
301030-40 parts of polyether;
21035-45 parts of polyether;
207012-17 parts of polyether;
4.5 parts of polyester PHN-563.5;
2.5-3.5 parts of diethylene glycol;
8190.3-0.35 part of photoinitiator;
CH-38-10 parts;
0.010-0.014 portion of phosphoric acid;
0.25 part of antioxidant PUR 680.15;
6220.1-0.2 part of light stabilizer;
the formula adopts MDI-100, MDI-50 and IPDI as compound raw materials of a mixture of mixed diisocyanate, the MDI has good mechanical property, high reaction activity and small volatility, although the yellowing resistance is poor, the cost is low, and the MDI can be used for products with low yellowing resistance requirements according to requirements to reduce the cost.
The preparation method of the light, heat and moisture cured PUR hot melt adhesive for textile use according to the embodiment of the second aspect of the invention comprises the following steps:
step S01, respectively dehydrating polyether polyol and polyester polyol under the dehydration conditions: the temperature is 120 ℃, the time is 2h, and the pressure is-0.09 MPa;
step S02, preheating and dehydrating the reaction kettle, adding diisocyanate, heating to 55 ℃, and uniformly stirring to obtain a diisocyanate mixture;
step S03, adding hydroxyl acrylate into the reaction kettle, introducing nitrogen for protection, heating to 80 ℃, and keeping for 2 hours;
step S04, cooling the temperature in the reaction kettle to 55 ℃, adding nitrogen for protection, adding the dehydrated polyether polyol obtained in the step S01 into the reaction kettle, adding phosphoric acid to control the reaction speed, reacting for 2 hours at 80 +/-2 ℃, then adding the dehydrated polyester polyol, and reacting for 40 minutes to obtain a prepolymer I;
step S05, adding a chain extender into the prepolymer I, reacting for 30min at 80 +/-2 ℃ to obtain a prepolymer II, and measuring the content of-NCO;
step S06, adding a photoinitiator, a light stabilizer, an antioxidant and an ultraviolet absorbent into the prepolymer II respectively, carrying out heat preservation reaction at 80-87 ℃ for 15-20min, uniformly stirring, and cooling to 50 ℃;
step S07, adding a latent curing agent into a reaction kettle, keeping the temperature at 50 ℃, and stirring for 15min to obtain the light, heat and moisture cured PUR hot melt adhesive for spinning;
according to the traditional preparation method, polyether and polyester are firstly added into a reaction kettle, and then isocyanate is added to react with the polyether and polyester, so that particles are easily generated in the preparation process, and the quality and the performance of the adhesive are influenced;
in the preparation process, the diisocyanate is added firstly, and then the polyether and the polyester are added, so that the problem that particles are easy to generate in the preparation process is effectively solved, and the quality of the adhesive is ensured.
Compared with the prior art, the invention has the beneficial technical effects that: the light, heat and moisture cured PUR hot melt adhesive for textile is cured by light, heat and moisture triple curing modes, and a CH-type curing agent is adopted, so that the curing speed is improved, the foaming problem in the PUR curing process is solved, the storage time is prolonged, and the preparation process is environment-friendly and pollution-free; in addition, the PUR hot-melt adhesive can also select yellowing-resistant raw materials such as HMDI, IPDI, HDI, polyether and polyester according to needs, effectively improves yellowing resistance of the PUR hot-melt adhesive, is particularly suitable for colored and light-colored textiles, enables the textiles to be bright in color and increases market competitiveness.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of the yellowing-resistant PUR hot melt adhesive in the embodiment of the application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention.
The technical scheme of the invention is further explained in detail by combining the drawings in the specification.
According to an embodiment of the first aspect of the invention:
example 1
A light, heat and moisture cured PUR hot melt adhesive for textiles comprises the following components in parts by mass:
30 parts of HMDI;
20 parts of IPDI;
10 parts of HDI;
12 parts of hydroxypropyl methacrylate;
301050 parts of polyether;
100040 parts of PTMEG;
207017 parts of polyether;
polyester Priplast 31927 parts;
5 parts of trimethylolpropane;
CH-48 parts;
0.014 part of phosphoric acid;
3790.25 parts of a photoinitiator;
10100.15 parts of an antioxidant;
7650.1 parts of light stabilizer;
and an ultraviolet absorbent UV-3280.3 parts.
Example 2
32 parts of HMDI;
IPDI 22.4 shares;
8.6 parts of HDI;
15 parts of hydroxypropyl methacrylate;
301040 portions of polyether;
100045 parts of PTMEG;
207015 parts of polyether;
polyester Priplast 31926 parts;
3.5 parts of trimethylolpropane;
CH-410 parts;
0.012 part of phosphoric acid;
3790.2 parts of a photoinitiator;
10100.15 parts of an antioxidant;
7650.2 parts of light stabilizer;
and an ultraviolet absorbent UV-3280.2 parts.
Example 3
32 parts of HMDI;
25 parts of IPDI;
7 parts of HDI;
17 parts of hydroxypropyl methacrylate;
301030 parts of polyether;
100050 parts of PTMEG;
207017 parts of polyether;
polyester Priplast 31925 parts;
3 parts of trimethylolpropane;
CH-412 parts;
0.010 part of phosphoric acid;
3790.15 parts of a photoinitiator;
10100.25 parts of an antioxidant;
7650.15 parts of light stabilizer;
and an ultraviolet absorbent UV-3280.15 parts.
According to an embodiment of the second aspect of the present invention, the preparation method of the yellowing-resistant PUR hot melt adhesive in the above embodiments 1 to 3 comprises the following steps:
step S01, polyether 3010, PTMEG-1000, polyether 2070 and Priplast3192 are respectively dehydrated under the conditions that: the temperature is 120 ℃, the time is 2h, and the pressure is-0.09 MPa;
step S02, preheating and dehydrating the reaction kettle, adding HMDI, IPDI and HDI into the reaction kettle, heating to 55 ℃, and uniformly stirring to obtain a diisocyanate mixture;
step S03, adding hydroxypropyl methacrylate into the reaction kettle, introducing nitrogen for protection, heating to 80 ℃, and keeping for 2 hours;
step S04, cooling the temperature in the reaction kettle to 55 ℃, adding nitrogen for protection, adding the polyether 3010 dehydrated in the step S01 into the reaction kettle, stirring for 10min, adding the dehydrated PTMEG-1000, and stirring for 20min, wherein the temperature in the reaction kettle rises;
adding dehydrated polyether 2070, adding phosphoric acid to control the reaction speed, reacting for 2 hours at 80 +/-2 ℃, then adding dehydrated PriPlast3192, and reacting for 40min to obtain prepolymer I;
step S05, adding trimethylolpropane into the prepolymer I, reacting for 30min at 80 +/-2 ℃ to obtain a prepolymer II, and measuring the content of-NCO;
step S06, adding a photoinitiator 379, a light stabilizer 765, an antioxidant 1010 and UV328 into the prepolymer II respectively, reacting at 80-87 ℃ for 15-20min, stirring uniformly, and cooling to 50 ℃;
and step S07, adding CH-4 into a reaction kettle, keeping the temperature at 50 ℃, and stirring for 15min to obtain the light, heat and moisture cured PUR hot melt adhesive for spinning.
Example 4
A light, heat and moisture cured PUR hot melt adhesive for textiles comprises the following components in parts by mass:
MDI-10026 parts;
MDI-5026 parts;
15 parts of IPDI;
17 parts of hydroxypropyl methacrylate;
301040 portions of polyether;
21045 parts of polyether;
207012 parts of polyether;
polyester PHN-563.5 parts;
3.5 parts of diethylene glycol;
8190.32 parts of a photoinitiator;
CH-39 parts;
0.014 part of phosphoric acid;
680.25 parts of antioxidant PUR;
6220.2 parts of light stabilizer.
Example 5
MDI-10025.6 parts;
MDI-5025.6 parts;
12.8 parts of IPDI;
15 parts of hydroxypropyl methacrylate;
301035 parts of polyether;
21040 parts of polyether;
207015 parts of polyether;
polyester PHN-564 parts;
3 parts of diethylene glycol;
8190.3 parts of a photoinitiator;
CH-310 parts;
0.012 part of phosphoric acid;
680.2 parts of antioxidant PUR;
6220.1 parts of light stabilizer.
Example 6
MDI-10026.5 parts;
MDI-5026.5 parts;
12 parts of IPDI;
12 parts of hydroxypropyl methacrylate;
301040 portions of polyether;
21045 parts of polyether;
207017 parts of polyether;
polyester PHN-564.5 parts;
2.5 parts of diethylene glycol;
8190.35 parts of a photoinitiator;
CH-310 parts;
0.010 part of phosphoric acid;
680.15 parts of antioxidant PUR;
6220.15 parts of light stabilizer.
According to the second aspect of the present invention, the preparation method of the low-cost PUR hot melt adhesive in the above embodiments 4 to 6 comprises the following steps:
step S01, respectively dehydrating polyether 3010, polyether 210, polyether 2070 and polyester PHN-56 under the dehydration conditions: the temperature is 120 ℃, the time is 2h, and the pressure is-0.09 MPa;
step S02, preheating and dehydrating the reaction kettle, adding MDI-100, MDI-50 and IPDI into the reaction kettle, heating to 55 ℃, and uniformly stirring to obtain a diisocyanate mixture;
step S03, adding hydroxypropyl methacrylate into the reaction kettle, introducing nitrogen for protection, heating to 80 ℃, and keeping for 2 hours;
step S04, cooling the temperature in the reaction kettle to 55 ℃, adding nitrogen for protection, adding the polyether 3010 dehydrated in the step S01 into the reaction kettle, stirring for reaction for 10min, adding the dehydrated polyether 2070, stirring for 10min, adding the dehydrated polyether 210, finally adding phosphoric acid to control the reaction speed, reacting for 2h at 80 +/-2 ℃, adding the dehydrated polyester PHN-56, and reacting for 40min to obtain a prepolymer I;
step S05, adding diethylene glycol into the prepolymer I, reacting for 30min at 80 +/-2 ℃ to obtain a prepolymer II, and measuring the content of-NCO;
step S06, respectively adding a photoinitiator 819, a light stabilizer 622 and an antioxidant PUR68 into the prepolymer II, carrying out heat preservation reaction at 80-87 ℃ for 15-20min, uniformly stirring, and cooling to 50 ℃;
and step S07, adding CH-3 into a reaction kettle, keeping the temperature at 50 ℃, and stirring for 15min to obtain the light, heat and moisture cured PUR hot melt adhesive for spinning.
The viscosities of the adhesives obtained in examples 1 to 6 were respectively measured, and the corresponding-NCO contents were calculated, with the following specific results:
TABLE 1 comparison of viscosity and-NCO content of adhesives of examples 1-6
| Numbering | Viscosity (mpa.s, 90 ℃, Brookfield viscometer) | -NCO content/%) |
| Example 1 | 9000-9500 | 3.56 |
| Example 2 | 5000-6000 | 4.17 |
| Example 3 | 5000-6000 | 4.12 |
| Example 4 | 8500-9000 | 3.77 |
| Example 5 | 5500-6000 | 4.14 |
| Example 6 | 3500-4500 | 4.33 |
As can be seen from Table 1, the-NCO contents of examples 1-6 were all between 3% and 5%, and the requirements of the PUR for the-NCO contents of the textile adhesives were satisfied.
The light, heat and moisture cured PUR hot melt adhesive for textile is cured by light, heat and moisture triple curing modes, and a CH-type curing agent is adopted, so that the curing speed is improved, the foaming problem in the PUR curing process is solved, the storage time is prolonged, and the preparation process is environment-friendly and pollution-free; in addition, the PUR hot-melt adhesive can also select yellowing-resistant raw materials such as HMDI, IPDI, HDI, polyether and polyester according to needs, effectively improves yellowing resistance of the PUR hot-melt adhesive, is particularly suitable for colored and light-colored textiles, enables the textiles to be bright in color and increases market competitiveness.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The light, heat and moisture cured PUR hot melt adhesive for textiles is characterized by comprising the following components:
57-74 parts of diisocyanate;
12-17 parts of hydroxyl acrylate;
77-117 parts of polyether polyol;
3.5-7 parts of polyester polyol;
2.5-5 parts of a chain extender;
8-12 parts of a latent curing agent;
0.01-0.014 part of phosphoric acid;
0.15-0.35 part of photoinitiator;
0.15-0.25 part of antioxidant;
0.1-0.2 part of light stabilizer;
0-0.3 part of ultraviolet absorbent.
2. The photo, thermal and moisture curable PUR hot melt adhesive for textile use according to claim 1, wherein the diisocyanate comprises aromatic and/or aliphatic, the aromatic diisocyanate comprises MDI-100 and MDI-50, and the aliphatic diisocyanate comprises IPDI, HDI and HMDI;
and the diisocyanate is a mixture of more than two of MDI-100, MDI-50, HMDI, HDI and IPDI.
3. The light, heat and moisture curable PUR hot melt adhesive for textile use according to claim 1, wherein the hydroxy acrylic monomer is β -hydroxyethyl acrylate or β -hydroxypropyl acrylate or hydroxyethyl methacrylate or hydroxypropyl methacrylate.
4. The light, heat and moisture curable PUR hot melt adhesive for textiles according to claim 1, wherein the polyether polyol is a mixture of polyether diol and polyether triol, the polyether diol is a mixture of at least two of PTMEG1000, polyether 2070 and polyether 210, and the polyether triol is polyether 3010.
5. The light, heat and moisture curable PUR hot melt adhesive for textile use according to claim 1, wherein the polyester polyol is polyester PHN-56 or polyester Priplast 3192.
6. The light, heat and moisture curable PUR hot melt adhesive for textiles as claimed in claim 1, wherein the chain extender is 1, 4-butanediol or trimethylolpropane or diethylene glycol.
7. The light, heat and moisture curable PUR hot melt adhesive for textile use according to claim 1, wherein the latent curing agent is a CH-type curing agent;
and/or the photoinitiator is photoinitiator 819 or photoinitiator 379 or photoinitiator 184;
and/or the antioxidant is antioxidant PUR68 or antioxidant 245 or antioxidant 1010;
and/or the light stabilizer is light stabilizer 692 or light stabilizer 765;
and/or the ultraviolet absorber is UV-327 or UV-328.
8. The light, heat and moisture cured PUR hot melt adhesive for textiles as claimed in claim 1, wherein the adhesive comprises the following components in parts by mass:
30-34 parts of HMDI;
20-30 parts of IPDI;
7-10 parts of HDI;
12-17 parts of hydroxypropyl methacrylate;
301030-50 parts of polyether;
PTMEG 100040-50 shares;
207012-17 parts of polyether;
polyester Priplast 31925-7 parts;
3-5 parts of trimethylolpropane;
CH-48-12 parts;
0.010-0.014 portion of phosphoric acid;
3790.15-0.25 part of photoinitiator;
10100.15-0.25 part of antioxidant;
7650.1-0.2 part of light stabilizer;
0.3 part of ultraviolet absorbent UV-3280.15;
wherein HMDI accounts for 50% of the total amount of HMDI, IPDI and HDI.
9. The light, heat and moisture cured PUR hot melt adhesive for textiles as claimed in claim 1, wherein the adhesive comprises the following components in parts by mass:
MDI-10023-28 parts;
MDI-5023-28 parts;
12-15 parts of IPDI;
12-17 parts of hydroxypropyl methacrylate;
301030-40 parts of polyether;
21035-45 parts of polyether;
207012-17 parts of polyether;
4.5 parts of polyester PHN-563.5;
2.5-3.5 parts of diethylene glycol;
8190.3-0.35 part of photoinitiator;
CH-38-10 parts;
0.010-0.014 portion of phosphoric acid;
0.25 part of antioxidant PUR 680.15;
0.2 part of light stabilizer 6220.1.
10. A process for preparing a light, heat and moisture curable PUR hot melt adhesive for textile use according to claim 1, comprising the steps of:
step S01, respectively dehydrating polyether polyol and polyester polyol under the dehydration conditions: the temperature is 120 ℃, the time is 2h, and the pressure is-0.09 MPa;
step S02, preheating and dehydrating the reaction kettle, adding diisocyanate, heating to 55 ℃, and uniformly stirring to obtain a diisocyanate mixture;
step S03, adding hydroxyl acrylate into the reaction kettle, introducing nitrogen for protection, heating to 80 ℃, and keeping for 2 hours;
step S04, cooling the temperature in the reaction kettle to 55 ℃, adding nitrogen for protection, adding the dehydrated polyether polyol obtained in the step S01 into the reaction kettle, adding phosphoric acid to control the reaction speed, reacting for 2 hours at 80 +/-2 ℃, then adding the dehydrated polyester polyol, and reacting for 40 minutes to obtain a prepolymer I;
step S05, adding a chain extender into the prepolymer I, reacting for 30min at 80 +/-2 ℃ to obtain a prepolymer II, and measuring the content of-NCO;
step S06, adding a photoinitiator, a light stabilizer, an antioxidant and an ultraviolet absorbent into the prepolymer II respectively, carrying out heat preservation reaction at 80-87 ℃ for 15-20min, uniformly stirring, and cooling to 50 ℃;
and S07, adding the latent curing agent into a reaction kettle, keeping the temperature at 50 ℃, and stirring for 15min to obtain the light, heat and moisture cured PUR hot melt adhesive for spinning.
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| CN114921218A (en) * | 2022-06-27 | 2022-08-19 | 山东一诺威聚氨酯股份有限公司 | UV (ultraviolet)/moisture dual-curing adhesive and preparation method thereof |
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