CN107880234A - A kind of preparation method of resistant to elevated temperatures polyurethane hot melt - Google Patents
A kind of preparation method of resistant to elevated temperatures polyurethane hot melt Download PDFInfo
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- CN107880234A CN107880234A CN201711200739.7A CN201711200739A CN107880234A CN 107880234 A CN107880234 A CN 107880234A CN 201711200739 A CN201711200739 A CN 201711200739A CN 107880234 A CN107880234 A CN 107880234A
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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
- C08G18/40—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/778—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur silicon
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The present invention relates to a kind of preparation method of resistant to elevated temperatures polyurethane hot melt, its polyurethane hot melt prepared is single-component mist-solidifying polyurethane adhesive, obtained PUR not only has good resistance to elevated temperatures, there is excellent cold-and-heat resistent impact, anti-drop toughness and good adhesive strength and salt spray resistance wet and heat ageing resistant performance simultaneously, the core competitiveness for lifting domestic polyurethane hot melt is had important practical significance.
Description
Technical field
The present invention relates to a kind of preparation method of polyurethane hot melt, more particularly to a kind of resistant to elevated temperatures polyurethane hot melt
Preparation method, belong to technical field of chemical adhesive.
Background technology
In recent years, with more attention of the people to environmental protection, environmentally friendly product is increasingly by universal pass
Note.Environmentally friendly adhesive with the advantage such as nontoxic, non-environmental-pollution, easy to use because being increasingly becoming following gluing
The development trend of agent.Reaction type polyurethane hot-melt adhesive (PUR) is used as a kind of high-performance environment protection type adhesive, and it is domestic and international right to have adapted to
The needs that environment is increasingly paid attention to.
Because PUR glue has, bonding is fast, nontoxic, technique is simple, there is preferable adhesive strength and flexible advantage again, because
This, extensive use is obtained in weaving, carpenter's furniture, car light, household electrical appliances and consumer electronics etc..
But traditional polyurethane hot melt exist one it is serious the defects of, i.e., resistance to elevated temperatures is poor.It is it is known that traditional
PUR is to be formed by polyester or polyether Glycols with di-isocyanate reaction, and molecular structure is substantially line style, and in its structure
The soft segment contained is more, therefore determines that traditional PUR is not applied for more than 100 DEG C of heatproof bonding requirements.
With expanding economy and the progress of science and technology, market is increasingly urgent to the PUR of high temperature resistant type demand, therefore, grinds
Send out resistant to elevated temperatures PUR adhesives a kind of, turn into the active demand in the field.
Resistant to elevated temperatures adhesives is researched and developed abroad to develop rapidly, but in China's starting than later, research and development institution is less, it is main
Will be including Darbond Technology Co., Ltd., Yantai etc..Therefore high temperature resistant type PUR research and development, market potential are huge.
The content of the invention
A kind of the shortcomings that present invention is directed to existing polyurethane hot melt resistance to elevated temperatures difference, there is provided resistant to elevated temperatures polyurethane heat
The preparation method of melten gel.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：
A kind of preparation method of resistant to elevated temperatures polyurethane hot melt, counts, comprises the following steps in parts by weight：
1) isocyanates 10~20 part of the average functionality more than 2.5 is added in reactor, keeps lazy in reactor
Property atmosphere, after be warming up to 60~80 DEG C, 0.3~3.0 part of silane modifier is added in backward reactor, is incubated under stirring condition
Reaction 1~3 hour, is made the isocyanate derivates that average functionality is 1.5~2.0, and adding chemistry in backward reactor removes
0.005~0.04 part of aqua is well mixed；
2) will be added to through pre- 7~20 parts of 1~5 part of diluent, the tackifying resin except water process anti-after step 1) terminates
Answer in kettle, inert atmosphere kept in reactor, after be warming up to 100~120 DEG C, stirring makes to add thereto after material is well mixed
Through pre- 6~20 parts of 25~45 parts of crystalline polyester polyols, PPG for removing water process, the insulation reaction under stirring condition
0.5~2 hour；
3) 15~35 parts of polyetheramine for removing water process in advance is added in the reactor after backward step 2) terminates, is protected in reactor
Inert atmosphere is held, is reacted 1~2 hour at 115~140 DEG C under stirring condition；
4) 0.01~0.2 part of catalyst is added in the reactor after terminating to step 3), vacuumizes removing bubble, is discharged,
Airtight package, produce.
The good principle of polyurethane hot melt resistance to elevated temperatures obtained by the inventive method is explained as follows：
1) the aromatic ring content for the isocyanates that we use is high, and heat resistance is good.The degree of functionality of the isocyanates of use is big
In 2.5, the degree of functionality of its NCO group is down to 2.0 or so with silane modifier, forms the NCO group of bifunctional structure, rear ginseng
With the chain extending reaction of polyalcohol.When be bonded solidify after, hydrolysis dealcoholysis occurs for the siloxanes of side chain, makes curing reaction to three-dimensional netted
Structural development, so as to form highdensity cross-linked structure, improve heat resistance.
2) using polyetheramine and NCO group chain extending reaction, the heat resistance for generating urea bond is higher than ammonia ester bond, while also effective
Ground improves the pliability, final adhesive strength and impact resistance of product.
3) using the PPG and polyetheramine of specific proportioning, ehter bond is introduced in strand, is effectively improved production
The pliability and impact resistance of product, avoid causing the drawbacks such as cracking, impact resistance difference because molecular structure rigidity is too strong, cause
Product fragility is too big.
4) crystalline polyester polyols that we use, have a special functionalized molecule structure, its active function groups with it is different
Polymerisation occurs for cyanate, effectively improves the crystallinity of PUR, improves the adhesive property of PUR.
5) polyalcohol used in the present invention mixes group by crystalline polyester polyols with noncrystalline PPG
Into initial strength can be improved by increasing the amount of crystalline polyester polyols, but crystallinity is excessive, and glue-line is fine and close, can hinder water
Vapour enters, and slows down curing rate；The amount of increase amorphism polyalcohol can extend the open hour, but initial strength can drop
It is low.Therefore need to balance the dosage of various polyalcohols, to obtain good performance.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
Further, the isocyanates is poly methylene poly phenyl poly isocyanate (PAPI), the isocyanide of triphenyl methane three
Any one in acid esters (TTI), 2,4- toluene diisocyanate trimers, HDI (HDI) tripolymer, it is excellent
Elect the commercially available MR-200 of the commercially available PM-200 of Yantai Wanhua limited company, Mitsui chemical company as and Bayer Bitterfeld GmbH is public
The one or more of mixtures taken charge of in commercially available HDI trimer Desmodur N3300.
Further, the silane modifier is mercaptopropyltriethoxysilane (KH-580), mercaptopropyl trimethoxysilane
(KH-590), second diaminopropyl trimethoxy silane (KH-792), N- phenyl-γ-aminopropyltrimethoxysilane (Y-
9669) one or more of compoundings in.
Further, the polyetheramine is that the copolymerization ether diamine containing Amino End Group, polytetramethylene ether diol PTMEG are main chain
Fragrant amino end group polyether diamine in any one, preferably U.S.'s Hensel advanced in years D230, EC301 of German BASF is beautiful
One kind in the aerochemical Versalink P-250 of state.
Further, the crystalline polyester polyols are polytetrahydrofuran diol or adipic acid and BDO, second
One kind in the product that at least one of glycol, diethylene glycol (DEG), 1,6- hexylene glycols dihydric alcohol is polymerized, described poly- tetrahydrochysene furan
Glycol of muttering is PTMEG-200, PTMEG-300, and the polyhexamethylene adipate glycol is preferably Jiangsu city of Xu Chuan chemical companies
The XCP-3000H sold, the polyadipate-BDO esterdiol are preferably that Qingdao New Yutian Chemical Co., Ltd. is commercially available
POL-356T。
Further, the PPG is polyoxypropyleneglycol of the molecular weight between 400~700g/mol, polyoxygenated
One kind in propylene-ethylene oxide glycol, the big DL-400 in preferably commercially available blue star east, Plant of Tianjin Petrochemical Company PPG204, PPG206,
One or both of PPG207 mixture.
Further, the catalyst is dibutyl tin laurate, stannous octoate, lead octoate, triethylamine, triethylene two
One kind in amine, cobalt octoate, zinc naphthenate, tetrabutyl titanate or dimorpholine base Anaesthetie Ether (DMDEE).
Further, the chemical deicer is to Methyl benzenesulfonyl hydrazine isocyanates (PTSI), triethyl orthoformate, oxazoles
One or more of compoundings in hydride compounds.
Further, the diluent is diisopropyl naphthalene, preferably German Johanna Lüttge company Ruetasolv DI.
Further, the tackifying resin is in phenolic resin, terpene resin, newtrex, acrylic resin, Petropols
One or more of compoundings, preferably chemical research institute of Shanxi Province octyl phenolic TXN-203, the stone of German Johanna Lüttge company
Oleoresin Novares LA700P, 2602 xylene resins of Shandong holy well chemical industry.
Polyurethane hot melt obtained by the method for the present invention is in addition to excellent resistance to elevated temperatures, also with following several
Big advantage：(1) good toughness and adhesive strength, the influence of the expansion coefficient difference between different materials, stress point can be overcome
Cloth is uniform, so as to be bonded different types of base material；(2) excellent cold-and-heat resistent impact：In -40 DEG C to+100 DEG C thermal shocks
Case, without cracking phenomena after 24 circulations；(3) viscosity is low easy to operate：100 DEG C of melting viscosities are less than 7Pa.S；(4) heat endurance is good：
120 DEG C of heating, 5 hours viscosity lift-off values are less than 30%；(5) anti-dropping capability is good：Roller drop test, 1000 times without cracking；
(6) final adhesive strength is high：PC is higher than 10.0MPa with PET material adhesive strength.
Embodiment
The principle and feature of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.
Raw material in following examples is parts by weight；Polyfunctionality isocyanates PM-200 is city of Yantai Wanhua company
Sell；Desmodur N3300 are that Bayer A.G is commercially available；Polyfunctionality isocyanates MR-200 is Mitsui chemical company
It is commercially available；PPG PPG204, PPG PPG207 are that the factory of Plant of Tianjin Petrochemical Company three is commercially available；PEPA POL-356T is
Qingdao New Yutian Chemical Co., Ltd. is commercially available；PEPA XCP-3000H is that Jiangsu Xu Chuan chemical companies are commercially available, and its hydroxyl value is
35~39mgKOH/g, acid number are 0.1~0.8mgKOH/g；Polyetheramine D230 is that Huntsman Corporation of the U.S. is commercially available, polyetheramine
EC301 is that BASF Aktiengesellschaft is commercially available, and polyetheramine Versalink P-250 are U.S.'s aerochemistry companies market.
Embodiment 1：
1) polyfunctionality isocyanates PM-200 is counted in 15 parts of addition reactors, be warming up under conditions of nitrogen protection
80 DEG C, 3.0 parts of silane modifier mercaptopropyl trimethoxysilane (KH-590) meter is added into reactor, with 700 revs/min
Rotating speed stirs, insulation reaction 1 hour, and isocyanate derivates of the average functionality 1.7 are made.After reaction terminates, to reaction
It is well mixed that 0.04 part of triethyl orthoformate is added in kettle；
2) 1 part of diisopropyl naphthalene (DI), 13 parts of 2602 xylene formaldehyde resin for removing water process in advance are added into reactor,
Be warming up to 120 DEG C under nitrogen protective condition, stirring is well mixed material, after add the crystallinity for removing water process in advance thereto
PEPA PTMEG-300 counts 25 parts, 20 parts of PPG PPG-204 meters, is protected so that 400 revs/min of rotating speed stirring is lower
Temperature reaction 20 minutes 1 hour；
3) added in the reactor after terminating to step 2) in advance except the polyetheramine Versalink P-250 meters 35 of water process
Part, nitrogen charging gas shielded in reactor, stirred with 900 revs/min of rotating speed, be maintained at 115 DEG C and react 1 hour；
4) 0.2 part of catalyst of triethylamine is added in the reactor after terminating to step 3), vacuumizes removing bubble, is discharged,
Airtight package, resistant to elevated temperatures polyurethane hot melt is made.
Embodiment 2：
1) polyfunctionality isocyanates Desmodur N3300 are counted in 10 parts of addition reactors, in the condition of nitrogen protection
Under be warming up to 70 DEG C, silane modifier N- phenyl-γ-aminopropyltrimethoxysilane (Y-9669) meter is added into reactor
1.6 parts, stirred with 550 revs/min of rotating speed, insulation reaction 3 hours, the isocyanates that average functionality is made 1.85 derives
Thing.After reaction terminates, into reactor, addition deicer is well mixed to Methyl benzenesulfonyl hydrazine isocyanates PTSI0.03 parts；
2) added into reactor in advance except 5 parts of the diisopropyl naphthalene (DI) of water process, phenolic resin TXN-203 count 7 parts, in
Be warming up to 110 DEG C under nitrogen protective condition, stirring is well mixed material, after add thereto in advance except the crystallinity of water process is gathered
Ester polyol XCP-3000H counts 36 parts, 14 parts of PPG DL-400 meters, anti-with 600 revs/min of the lower insulation of rotating speed stirring
Answer 2 hours；
3) add in the reactor after terminating to step 2) in advance except the polyetheramine D230 of water process counts 25 parts, filled in reactor
Nitrogen is protected, and is stirred with 700 revs/min of rotating speed, is maintained at 130 DEG C and reacts 1.5 hours；
4) 0.11 part of catalyst dimorpholine base Anaesthetie Ether DMDEE is added in the reactor after terminating to step 3), is taken out true
Sky removing bubble, discharging, airtight package, is made resistant to elevated temperatures polyurethane hot melt.
Embodiment 3：
1) polyfunctionality isocyanates MR-200 is counted in 20 parts of addition reactors, be warming up under conditions of nitrogen protection
60 DEG C, 0.3 part of silane modifier second diaminopropyl trimethoxy silicon KH-792 meters are added into reactor, with 400 revs/min
Rotating speed stirring, insulation reaction 2 hours, isocyanate derivates of the average functionality 2.0 are made.After reaction terminates, to anti-
Answer in kettle plus enter 0.005 part of oxazole alkanes deicer and be well mixed；
2) added into reactor in advance except 3 parts of the diisopropyl naphthalene (DI) of water process, Petropols LA700P count 20 parts, in
Be warming up to 100 DEG C under nitrogen protective condition, stirring is well mixed material, after add thereto in advance except the crystallinity of water process is gathered
Ester polyol POL-356T counts 45 parts, 6 parts of PPG PPG-207 meters, anti-with 700 revs/min of the lower insulation of rotating speed stirring
Answer 0.5 hour；
3) added in the reactor after terminating to step 2) in advance except the polyetheramine EC-301 of water process counts 15 parts, in reactor
Nitrogen charging gas shielded, stirred with 1100 revs/min of rotating speed, be maintained at 140 DEG C and react 2 hours；
4) 0.01 part of catalyst dibutyltin dilaurylate is added in the reactor after terminating to step 3), vacuumizes removing
Bubble, discharging, airtight package, resistant to elevated temperatures polyurethane hot melt is made.
Embodiment 4：
1) polyfunctionality isocyanates PM-200 is counted in 15 parts of addition reactors, be warming up under conditions of nitrogen protection
80 DEG C, 3.0 parts of silane modifier mercaptopropyl trimethoxysilane (KH-590) meter is added into reactor, with 700 revs/min
Rotating speed stirs, insulation reaction 1 hour, and isocyanate derivates of the average functionality 1.7 are made.After reaction terminates, to reaction
It is well mixed that 0.04 part of triethyl orthoformate is added in kettle；
2) 13 parts of 1 part of diisopropyl naphthalene (DI), newtrex for removing water process in advance are added into reactor, is protected in nitrogen
Under the conditions of be warming up to 120 DEG C, stirring is well mixed material, after add the crystalline polyester polyols for removing water process in advance thereto
PTMEG-300 counts 25 parts, 20 parts of PPG PPG-204 meters, and lower insulation reaction is stirred 1 hour with 400 revs/min of rotating speed
20 minutes；
3) added in the reactor after terminating to step 2) in advance except the polyetheramine Versalink P-250 meters 35 of water process
Part, nitrogen charging gas shielded in reactor, stirred with 900 revs/min of rotating speed, be maintained at 115 DEG C and react 1 hour；
4) 0.2 part of octoate catalyst lead is added in the reactor after terminating to step 3), vacuumizes removing bubble, is discharged,
Airtight package, resistant to elevated temperatures polyurethane hot melt is made.
Embodiment 5：
1) polyfunctionality isocyanates Desmodur N3300 are counted in 10 parts of addition reactors, in the condition of nitrogen protection
Under be warming up to 70 DEG C, silane modifier N- phenyl-γ-aminopropyltrimethoxysilane (Y-9669) meter is added into reactor
1.6 parts, stirred with 550 revs/min of rotating speed, insulation reaction 3 hours, the isocyanates that average functionality is made 1.85 derives
Thing.After reaction terminates, into reactor, addition deicer is well mixed to Methyl benzenesulfonyl hydrazine isocyanates PTSI0.03 parts；
2) 7 parts of 5 parts of diisopropyl naphthalene (DI), acrylic resin meter for removing water process in advance are added into reactor, in nitrogen
Be warming up to 110 DEG C under protective condition, stirring is well mixed material, after add thereto in advance except the crystalline polyester of water process is more
First alcohol XCP-3000H counts 36 parts, 14 parts of PPG DL-400 meters, with 600 revs/min of the lower insulation reaction 2 of rotating speed stirring
Hour；
3) add in the reactor after terminating to step 2) in advance except the polyetheramine D230 of water process counts 25 parts, filled in reactor
Nitrogen is protected, and is stirred with 700 revs/min of rotating speed, is maintained at 130 DEG C and reacts 1.5 hours；
4) 0.11 part of catalyst tetrabutyl titanate is added in the reactor after terminating to step 3), vacuumizes removing gas
Bubble, discharging, airtight package, resistant to elevated temperatures polyurethane hot melt is made.
Comparative example：
The formula and processing technology of traditional moisture-curable PUR glue is as follows：PPG PPG210 is counted 20 parts, polyester is more
First alcohol POL-356T is counted in 45 parts of addition reactors, is stirred with 500 revs/min of rotating speed, vacuum dehydration 2 hours at 120 DEG C,
Vacuum is maintained at -0.09MPa.Then 80 DEG C are cooled to, side stirring is counted all over 4,4' methyl diphenylene diisocyanates MDI is added
15 parts, then slowly heating, control temperature is at 80 DEG C, while nitrogen charging gas shielded, reacts 2.5 hours.Analysis NCO% to be sampled contains
After amount reaches design load, 15 parts of terpenes tackifying resin, 0.1 part of catalyst dibutyltin dilaurylate and triethylene diamine are added
0.4 part.Bubble-free is evacuated under conditions of being 110 DEG C in temperature, then discharges, airtight package, places stand-by.This glue is in work
For skill in use, first opening heating system, temperature setting is 100~130 DEG C, and with glue rifle gluing, gluing process is ensured when opening
Interior completion, then test is carried out in accordance with regulations.Resistance to elevated temperatures, cold-and-heat resistent impact property, anti-drop toughness, adhesive strength and moisture-proof
Heat aging performance, tested after being placed 7 days by room temperature after applying glue.General cold curing can reach maximum intensity in 7 days.
In order to verify the technique effect of polyurethane hot melt obtained by the method for the present invention, we are by the gained of embodiment 1~3
Polyurethane hot melt carries out normal temperature shear strength, 90 with polyurethane hot melt prepared by comparative example by adhesive testing standard
DEG C immediately shear strength, tensile strength, elongation at break, cold-and-heat resistent impact property, roller drop test, salt spray test and double 85
Burn-in test, data result is as shown in table 1, table 2, table 3.
Wherein with the ratio between the numerical value of 90 DEG C of instant shear strengths and numerical value of normal temperature shear strength, elevated temperature strength guarantor is calculated
Holdup, the resistance to elevated temperatures of glue is characterized according to the numerical values recited of elevated temperature strength conservation rate, this is that the core of the present invention considers finger
Mark.In addition, pliability of the present invention, adhesive strength, cold-and-heat resistent impact property, anti-drop toughness are respectively by the stretching of table 2
Intensity, elongation at break, normal temperature shear strength, roller drop test, the numerical value of cold-and-heat resistent impact property are characterized；Salt spray resistance
Characterized with wet and heat ageing resistant performance by the numerical value of the detection project of table 3.
The embodiment 1~3 of table 1 and the resistance to elevated temperatures test comparison of comparative example products obtained therefrom
The embodiment 1~3 of table 2 compares with the measuring mechanical property of comparative example products obtained therefrom
The embodiment 1~3 of table 3 and the water-fast ageing-resistant performance test comparison of comparative example products obtained therefrom
In a word, shown by the performance test analysis of the embodiment 1~3 and comparative example listed in 1~table of table 3, this hair
The polyurethane hot melt of bright preparation not only has a good resistance to elevated temperatures, at the same the glue have excellent cold-and-heat resistent impact,
Anti-drop toughness and good adhesive strength and salt spray resistance wet and heat ageing resistant performance.So polyurethane provided by the present invention
PUR, the bonding demand of specific hot environment is disclosure satisfy that, had to the core competitiveness for lifting domestic polyurethane hot melt
Important realistic meaning.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (10)
- A kind of 1. preparation method of resistant to elevated temperatures polyurethane hot melt, it is characterised in that count in parts by weight, including following step Suddenly：1) isocyanates 10~20 part of the average functionality more than 2.5 is added in reactor, inertia atmosphere is kept in reactor Enclose, be warming up to 60~80 DEG C, 0.3~3.0 part of silane modifier, insulation reaction 1 under stirring condition are added in backward reactor ~3 hours, the isocyanate derivates that average functionality is 1.5~2.0 are made, chemical deicer is added in backward reactor 0.005~0.04 part well mixed；2) reactor after step 1) terminates will be added to through 7~20 parts of 1~5 part of diluent, the tackifying resin in advance except water process In, inert atmosphere is kept in reactor, after be warming up to 100~120 DEG C, stirring adds through pre- thereto after making material well mixed Except 6~20 parts of 25~45 parts of crystalline polyester polyols, the PPG of water process, insulation reaction 0.5 under stirring condition ~2 hours；3) 15~35 parts of polyetheramine for removing water process in advance is added in the reactor after backward step 2) terminates, keeps lazy in reactor Property atmosphere, reacted 1~2 hour at 115~140 DEG C under stirring condition；4) 0.01~0.2 part of catalyst is added in the reactor after terminating to step 3), vacuumizes removing bubble, is discharged, it is closed Packaging, is produced.
- 2. preparation method according to claim 1, it is characterised in that the isocyanates is polymethylene polyphenyl polyisocyanate In cyanate, triphenylmethane triisocyanate, 2,4 toluene diisocyanate tripolymer, HDI tripolymer Any one.
- 3. preparation method according to claim 1, it is characterised in that the silane modifier is mercapto propyl-triethoxysilicane In alkane, mercaptopropyl trimethoxysilane, second diaminopropyl trimethoxy silane, N- phenyl-γ-aminopropyltrimethoxysilane One or more of compoundings.
- 4. preparation method according to claim 1, it is characterised in that the polyetheramine is the copolyether two containing Amino End Group Amine, polytetramethylene ether diol PTMEG are any one in the polyether diamine of the fragrant amino end group of main chain.
- 5. preparation method according to claim 1, it is characterised in that the crystalline polyester polyols are PolyTHF Glycol or adipic acid are polymerized with least one of 1,4- butanediols, ethylene glycol, diethylene glycol (DEG), 1,6-HD dihydric alcohol Product in one kind.
- 6. preparation method according to claim 1, it is characterised in that the PPG be molecular weight between 400~ One kind in 700g/mol polyoxypropyleneglycol, PPOX-ethylene oxide glycol.
- 7. preparation method according to claim 1, it is characterised in that the catalyst is dibutyl tin laurate, pungent Sour stannous, lead octoate, triethylamine, triethylenediamine, cobalt octoate, zinc naphthenate, tetrabutyl titanate or dimorpholine base diethyl One kind in base ether.
- 8. according to the preparation method any one of claim 1-7, it is characterised in that the chemical deicer is to methyl One or more of compoundings in benzene sulfonyl hydrazide isocyanates, triethyl orthoformate, oxazole hydride compounds.
- 9. according to the preparation method any one of claim 1-7, it is characterised in that the diluent is diisopropyl Naphthalene.
- 10. according to the preparation method any one of claim 1-7, it is characterised in that the tackifying resin is phenolic aldehyde tree One or more of compoundings in fat, terpene resin, newtrex, acrylic resin, Petropols.
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| CN108949090A (en) * | 2018-07-20 | 2018-12-07 | 安徽匠星联创新材料科技有限公司 | A kind of solvent-free dual-component polyurethane sealant and preparation method thereof |
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| CN110467898A (en) * | 2018-05-10 | 2019-11-19 | 上海本诺电子材料有限公司 | A kind of PUR adhesive and preparation method thereof |
| CN110699030A (en) * | 2019-10-11 | 2020-01-17 | 汕头市鑫源化工科技有限公司 | Electrostatic flocking adhesive and preparation method thereof |
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| CN111040712A (en) * | 2019-12-20 | 2020-04-21 | 烟台德邦科技有限公司 | Preparation method of high-strength sweat-resistant polyurethane hot melt adhesive |
| CN111087963A (en) * | 2019-12-27 | 2020-05-01 | 江苏乘鹰新材料股份有限公司 | Single-component solvent-free moisture-curing adhesive for compounding cigarette paperboard |
| CN111808569B (en) * | 2020-07-24 | 2021-11-23 | 山东北方现代化学工业有限公司 | Damp and heat resistant high-strength single-component polyurethane primer-free adhesive sealant and preparation method thereof |
| CN111808569A (en) * | 2020-07-24 | 2020-10-23 | 山东北方现代化学工业有限公司 | Damp and heat resistant high-strength single-component polyurethane primer-free adhesive sealant and preparation method thereof |
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Application publication date: 20180406 |