CN110041495A - A kind of manufacturing method of hot melt film thermoplastic polyurethane resin - Google Patents
A kind of manufacturing method of hot melt film thermoplastic polyurethane resin Download PDFInfo
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- CN110041495A CN110041495A CN201910400634.9A CN201910400634A CN110041495A CN 110041495 A CN110041495 A CN 110041495A CN 201910400634 A CN201910400634 A CN 201910400634A CN 110041495 A CN110041495 A CN 110041495A
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- hot melt
- melt film
- polyurethane resin
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- thermoplastic polyurethane
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/65—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
-
- 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
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- 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
- C09J2475/00—Presence of polyurethane
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a kind of manufacturing method of hot melt film thermoplastic polyurethane resin; it include: by low molecular weight polyvalent alcohol at 60 120 DEG C of temperature; vacuum degree is to be dehydrated 1-3h under -0.06MPa -0.095MPa; moisture content is measured less than 0.1%; release vacuum; chain extender and stabilizer are put into reaction kettle; wherein polyvalent alcohol accounts for 45% the 85% of total amount of feeding; chain extender is 5% the 40% of total amount of feeding; stabilizer is 0.1% the 2% of total amount of feeding; it stirs at low speed 2-4h to be uniformly mixed, in the process nitrogen protection；Then after one or more dicyanates being heated to 50 70 DEG C, with above-mentioned material after mixed at high speed, into in mixing reactor, in 60 200 DEG C of 3 10min of thermotonus, finally it is granulated to obtain finished product, catalyst is added according to reactivity degree, compared with prior art, for the present invention with following the utility model has the advantages that product index is suitable, crystal point amount is controllable, different batches of product quality is stablized, and technological fluctuation and equipment adjustment in hot melt film production process are reduced.
Description
Technical field
The present invention is a kind of manufacturing method of hot melt film thermoplastic polyurethane resin.
Background technique
Hot melt film has that binding speed is fast, nontoxic, adhesion technique is simple, and has preferable adhesion strength and flexibility, because
This is mainly used in garment material, and metal, timber, the bonding of the materials such as plastics, big with bonding plane bonding area, glue-spread is equal
It is even to bond the features such as smooth.Hot melt film use reliability is high, and adhesion technique is easy, and waste is few, and mixed problem is not present, can reach
Preferred physical performance.
Thermoplastic polyurethane resin (TPU) is one kind by low molecular weight polyvalent alcohol soft segment and diisocyanate-chain extender
The linear polymer that hard section is constituted has excellent physical property, good weatherability, the bonding adaptability to a variety of substrates
The advantages that.And due to the diversity of its formula, and allow to the adhesive as various material, especially in hot melt film field
Application is rapid.
TPU hot melt film processing technology has fusion method and solwution method, and melt-processed is that TPU resin particle plastics industry is normal
Technique: it is such as kneaded, calendering, squeezes out, be blow molded and mold, addition solvent is not needed in processing technology.Solution processing is by TPU
Resin particle is dissolved in solvent or directly polymerize in a solvent and solution is made and coated, be film-made again.
Requirement of the general hot melt film production to TPU resin is that fusing point is up to standard, and process stabilizing, crystal point amount is few, stablizes between batch.Heat
Melt film generally uses bulk polymerization or solution polymerization process with polyurethane resin.It is limited to current China's polyurethane industries among others developing water
Flat, some polyurethane resin manufacturers production equipment more falls behind, and corollary equipment is incomplete, and product quality management control level is not
Height, production technology level of aggregation still has no small gap compared with external enterprise, thus domestic TPU resin is generally existing at present
Technological fluctuation is big, crystal point quantity difficulty control, and stability is poor between batch, and for hot melt film manufacturer, these problems are directly influenced
The quality of production of hot melt film is stablized.Domestic TPU resin is only used for low-grade hot melt film product, for medium-to-high grade hot melt film product,
External TPU resin excellent combination property, stay in grade, supply falls short of demand.Nevertheless, foreign countries' TPU resin price is expensive, the supply of material is not
Stablize, vulnerable to restriction of trade etc., restricts the development of domestic industries.
Summary of the invention
In view of the deficienciess of the prior art, it is an object of the present invention to provide a kind of hot melt film thermoplastic polyurethane resin
Manufacturing method, to solve the problems mentioned in the above background technology.
To achieve the goals above, the present invention is to realize by the following technical solutions: a kind of hot melt film thermoplasticity
The manufacturing method of polyurethane resin, comprising:
By low molecular weight polyvalent alcohol at 60 120 DEG C of temperature, vacuum degree is to be dehydrated 1-3h under -0.06MPa -0.095MPa,
Moisture content is measured less than 0.1%, vacuum is released, chain extender and stabilizer is put into reaction kettle, wherein polyvalent alcohol Zhan is total
45% the 85% of inventory, chain extender are 5% the 40% of total amount of feeding, and stabilizer is 0.1% the 2% of total amount of feeding, and low speed stirs
It mixes 2-4h to be uniformly mixed, in the process nitrogen protection；
Then after one or more dicyanates being heated to 50 70 DEG C, with above-mentioned material after mixed at high speed, into mixing
In reactor, in 60 200 DEG C of 3 10min of thermotonus, finally it is granulated to obtain finished product, is added according to reactivity degree
Enter catalyst.
Further, the low molecular weight polyvalent alcohol is the polyester diol, flat that average molecular weight is 600 6000
The one or two kinds of mixing for the polyether Glycols that average molecular weight is 500 2000.
Further, the chain extender is ethylene glycol, 1,4-butanediol, 1,3-PD, 1,6- hexylene glycol, methyl-prop
The mixing of one or more of glycol, neopentyl glycol.
Further, the diisocyanate is toluene di-isocyanate(TDI), 4,4 '-methyl diphenylene diisocyanates,
The mixing of one or more of isophorone diisocyanate, hexamethylene diisocyanate, the additional amount of diisocyanate with
The molal quantity meter of isocyanate group, polyvalent alcohol is in terms of the molal quantity of hydroxyl, the molar ratio of isocyanate group and hydroxyl, i.e. r value,
It is 0.95 1.05, the dosage of catalyst accounts between 0.01% the 0.1% of polyurethane gross mass.
Further, the catalyst is triethylenediamine, stannous octoate, dibutyl tin dilaurate, protochloride
One or more of mixing of tin.
Further, the mixing reactor is casting mixing apparatus, double screw extruder, in single screw extrusion machine
It is a kind of.
Beneficial effects of the present invention: a kind of manufacturing method of hot melt film thermoplastic polyurethane resin of the invention, product
Index is suitable, and crystal point amount is controllable, and different batches of product quality is stablized, and reduces technological fluctuation and equipment tune in hot melt film production process
It is whole.
Specific embodiment
To be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, below with reference to
Specific embodiment, the present invention is further explained.
The present invention provides a kind of technical solution: a kind of manufacturing method of hot melt film thermoplastic polyurethane resin, comprising:
By low molecular weight polyvalent alcohol at 60 120 DEG C of temperature, vacuum degree is to be dehydrated 1-3h under -0.06MPa -0.095MPa,
Moisture content is measured less than 0.1%, vacuum is released, chain extender and stabilizer is put into reaction kettle, wherein polyvalent alcohol Zhan is total
45% the 85% of inventory, chain extender are 5% the 40% of total amount of feeding, and stabilizer is 0.1% the 2% of total amount of feeding, and low speed stirs
It mixes 2-4h to be uniformly mixed, in the process nitrogen protection；
Then after one or more dicyanates being heated to 50 70 DEG C, with above-mentioned material after mixed at high speed, into mixing
In reactor, in 60 200 DEG C of 3 10min of thermotonus, finally it is granulated to obtain finished product, is added according to reactivity degree
Enter catalyst.
Further, the low molecular weight polyvalent alcohol is the polyester diol, flat that average molecular weight is 600 6000
The one or two kinds of mixing for the polyether Glycols that average molecular weight is 500 2000.
Further, the chain extender is ethylene glycol, 1,4-butanediol, 1,3-PD, 1,6- hexylene glycol, methyl-prop
The mixing of one or more of glycol, neopentyl glycol.
Further, the diisocyanate is toluene di-isocyanate(TDI), 4,4 '-methyl diphenylene diisocyanates,
The mixing of one or more of isophorone diisocyanate, hexamethylene diisocyanate, the additional amount of diisocyanate with
The molal quantity meter of isocyanate group, polyvalent alcohol is in terms of the molal quantity of hydroxyl, the molar ratio of isocyanate group and hydroxyl, i.e. r value,
It is 0.95 1.05, the dosage of catalyst accounts between 0.01% the 0.1% of polyurethane gross mass.
Further, the catalyst is triethylenediamine, stannous octoate, dibutyl tin dilaurate, protochloride
One or more of mixing of tin.
Further, the mixing reactor is casting mixing apparatus, double screw extruder, in single screw extrusion machine
It is a kind of.
As an embodiment of the present invention: by method integrated use, the TPU resin of production can be made to have following
Advantage:
1. having suitable product to process index, it is suitable for hot melt film melt-processed technique.
2. having the index requests such as fusing point, hardness needed for meeting different hot melt films, thus there is suitable surface drying speed
And resistance to blocking, it is suitable for hot melt film and winds.
3. volatilizable organic matter is free of, not plasticizer-containing, in process, as long as having corresponding ventilation equipment, no
It can cause environmental pollution, safe operation, be not necessarily to explosion precaution.
4. moisture content meets the requirement of hot melt film processing technology, do not need further to dry, saves process time and the energy
Consumption, reduces the production cycle, reduces cost.
5. product index is suitable, crystal point amount is controllable, and different batches of product quality is stablized, and reduces work in hot melt film production process
Skill fluctuation and equipment adjustment.
As an embodiment of the present invention: example 1: by the polyhexamethylene adipate glycol of average molecular weight 2000
200kg, average molecular weight 1000 polyhexamethylene adipate glycol 100kg1,4- butanediol 9.2kg and stabilizer 0.8kg add
Enter in 1 cube of reaction kettle, the kettle is with stirring, temperature control system and vacuum system.At vacuum degree -0.095MPa, temperature control
System is surveyed its water and is lower than under 0.1% in 100 120 DEG C of dehydration 2h.80 DEG C are down to, nitrogen protection.
4,4'- methyl diphenylene diisocyanate (MDI) is heated uniformly to 55 DEG C, nitrogen protection.By mixed at high speed
Double-screw reactor is added after mixing MDI and said mixture in head, and it is 70 ~ 180 DEG C that each section of reaction temperature, which is arranged, and control stops
Time response pelletizing in 23 minutes is stayed, after after post treatment, surveys its performance after placing 24 hours.
The technological parameters such as monitoring temperature and mass flow ratio in production process measure product Melt Viscosity and crystal point amount etc.
Index adjusts in time, guarantees that production is stablized.
Respectively according to national standards GB_2411-1980, GBT_4507-1999, GBT3682-2000 to hardness, softening point,
Melt index is detected.Corresponding test specimen is made in resin, carries out the measurement of T-type peel strength according to GB/T2791-1995.It presses
According to enterprise's internal control method, resin crystal point quantity is measured.It measures as a result, hardness 88A, 124 DEG C of softening point, melt index 18.6g/
10min(5.0kg, 160 DEG C), measure 15/10 grams of crystal point quantity, the above index has reached a kind of hot melt film TPU resin
It is required that.
As an embodiment of the present invention: by the polybutylene glyool adipate 1000kg of average molecular weight 3000,
1,6- hexylene glycol 59.0kg and stabilizer 5.0kg is added in 3 cubes of reaction kettle, and the kettle is with stirring, temperature control system and vacuum
System.In vacuum degree -0.095MPa, temperature control is surveyed its water and is lower than under 0.1% in 100 120 DEG C of dehydration 2h.It is down to 90
DEG C, the stannous chloride solution (20% content) of 80mL is added in the mixture of Xiang Shangshu, mixes 2h, nitrogen protection.
4,4'- methyl diphenylene diisocyanate (MDI) is heated uniformly to 65 DEG C, nitrogen protection.By mixed at high speed
Double-screw reactor is added after mixing MDI and said mixture in head, and it is 90 200 DEG C of reaction temperature that each section of reaction temperature, which is arranged,
The degree control residence time reacts pelletizing in 45 minutes, after after post treatment, surveys its performance after placing 24 hours.
Production process control and product quality detection are identical with example 1.
Measuring product index is, hardness 97A, 120 DEG C of softening point, melt index 10.6g/10min(5.0kg, 160 DEG C),
20/10 grams of crystal point quantity are measured, the above index has reached a kind of requirement of hot melt film TPU resin, specific index such as table 1.
Table 1
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention, for those skilled in the art
For member, it is clear that invention is not limited to the details of the above exemplary embodiments, and without departing substantially from spirit of the invention or substantially
In the case where feature, the present invention can be realized in other specific forms.Therefore, in all respects, should all will implement
Example regards exemplary as, and is non-limiting, and the scope of the present invention is by appended claims rather than above description limits
It is fixed, it is intended that including all changes that fall within the meaning and scope of the equivalent elements of the claims in the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (6)
1. a kind of manufacturing method of hot melt film thermoplastic polyurethane resin, it is characterised in that: include:
By low molecular weight polyvalent alcohol at 60 120 DEG C of temperature, vacuum degree is to be dehydrated 1-3h under -0.06MPa -0.095MPa,
Moisture content is measured less than 0.1%, vacuum is released, chain extender and stabilizer is put into reaction kettle, wherein polyvalent alcohol Zhan is total
45% the 85% of inventory, chain extender are 5% the 40% of total amount of feeding, and stabilizer is 0.1% the 2% of total amount of feeding, and low speed stirs
It mixes 2-4h to be uniformly mixed, in the process nitrogen protection；
Then after one or more dicyanates being heated to 50 70 DEG C, with above-mentioned material after mixed at high speed, into mixing
In reactor, in 60 200 DEG C of 3 10min of thermotonus, finally it is granulated to obtain finished product, is added according to reactivity degree
Enter catalyst.
2. a kind of manufacturing method of hot melt film thermoplastic polyurethane resin according to claim 1, it is characterised in that: institute
The low molecular weight polyvalent alcohol stated be average molecular weight be 600 6000 polyester diol, average molecular weight be 500 2000
Polyether Glycols one or two kinds of mixing.
3. a kind of manufacturing method of hot melt film thermoplastic polyurethane resin according to claim 1, it is characterised in that: institute
The chain extender stated is ethylene glycol, 1,4- butanediol, 1,3- propylene glycol, 1,6-HD, methyl propanediol, one in neopentyl glycol
Kind or several mixing.
4. a kind of manufacturing method of hot melt film thermoplastic polyurethane resin according to claim 1, it is characterised in that: institute
The diisocyanate stated is toluene di-isocyanate(TDI), 4,4 '-methyl diphenylene diisocyanates, isophorone diisocyanate,
The mixing of one or more of hexamethylene diisocyanate, the additional amount of diisocyanate is with the molal quantity of isocyanate group
Meter, polyvalent alcohol is in terms of the molal quantity of hydroxyl, the molar ratio of isocyanate group and hydroxyl, i.e. r value, is 0.95 1.05, catalysis
The dosage of agent accounts between 0.01% the 0.1% of polyurethane gross mass.
5. a kind of manufacturing method of hot melt film thermoplastic polyurethane resin according to claim 1, it is characterised in that: institute
The catalyst stated is one or more of mixing of triethylenediamine, stannous octoate, dibutyl tin dilaurate, stannous chloride.
6. a kind of manufacturing method of hot melt film thermoplastic polyurethane resin according to claim 1, it is characterised in that: institute
The mixing reactor stated is one of casting mixing apparatus, double screw extruder, single screw extrusion machine.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910400634.9A CN110041495A (en) | 2019-05-15 | 2019-05-15 | A kind of manufacturing method of hot melt film thermoplastic polyurethane resin |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910400634.9A CN110041495A (en) | 2019-05-15 | 2019-05-15 | A kind of manufacturing method of hot melt film thermoplastic polyurethane resin |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4962138A (en) * | 1988-05-27 | 1990-10-09 | W. R. Grace & Co.-Conn. | Reactive hot melt structural adhesive |
| CN103059245A (en) * | 2012-12-13 | 2013-04-24 | 洛阳吉明化工有限公司 | Preparation method of polyurethane used for high strength hot melting adhesive membrane |
| CN104059214A (en) * | 2014-06-23 | 2014-09-24 | 奥斯汀新材料（张家港）有限公司 | Preparation method of high-hardness thermoplastic polyurethane elastomer |
-
2019
- 2019-05-15 CN CN201910400634.9A patent/CN110041495A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4962138A (en) * | 1988-05-27 | 1990-10-09 | W. R. Grace & Co.-Conn. | Reactive hot melt structural adhesive |
| CN103059245A (en) * | 2012-12-13 | 2013-04-24 | 洛阳吉明化工有限公司 | Preparation method of polyurethane used for high strength hot melting adhesive membrane |
| CN104059214A (en) * | 2014-06-23 | 2014-09-24 | 奥斯汀新材料（张家港）有限公司 | Preparation method of high-hardness thermoplastic polyurethane elastomer |
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