CN109609077A - Organic-silicon-modified reaction-type flame-retarding polyurethane hot melt and preparation method thereof - Google Patents
Organic-silicon-modified reaction-type flame-retarding polyurethane hot melt and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- 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
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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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
- C08G18/48—Polyethers
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of organic-silicon-modified reaction-type flame-retarding polyurethane hot melt and preparation method thereof, feature be the polyether Glycols for including 1~20 part, 1~35 part of liquid polyesters dihydric alcohol, 1~40 part of flame retardant polyether polyol, 1~35 part of crystalline polyester dihydric alcohol, 1~35 part containing isocyanate-modified poly-organosilicon acrylate copolymer, 1~40 part of isocyanates, 0.01~1 part of catalyst, 0.01~1 part of antioxidant and 0.1~2 part of silane coupling agent.The present invention pass through first radical polymerization synthesize it is poly- (methacryloxypropyl list block dimethyl polysiloxane-it is random-styrene-is random-methyl acrylate-is random-isocyanatoethyl), it is added in base polyurethane prepolymer for use as, introduce organic silicon acrylic ester copolymer segment and reactive flame retardant, Formulation Ingredients efficiently act synergistically, and improve hot melt adhesive chemicals-resistant and flame retardant property.
Description
Technical field
The invention belongs to structure glue technical fields, and in particular to a kind of organic-silicon-modified reaction-type flame-retarding polyurethane hot melt
And preparation method thereof, which are mainly applied to electronics and appliance industry, automobile industry, weaving and shoe industry, food packing industry, wood materials
Processing and furniture industry isostructuralism are bonded field.
Background technique
Polyurethane hot melt be a new generation can provide superior adhesion can structure glue, it is to be with polyurethane prepolymer
Material of main part is equipped with a hot melt adhesive prepared by various auxiliary agents.Polyurethane hot melt is easy to use and environmentally friendly, and performance again can be with
Solvent-based thermal melten gel compares favourably.Nearly ten years, polyurethane hot melt is obtained in the high-end fields such as electronics and appliance industry, automobile industry
It is fast-developing and be widely used.Polyurethane hot melt is different by cured form, can be divided into thermoplastic polyurethane elastomer hot melt
Glue and reactive polyurethane hot melt；Reactive polyurethane hot melt is different by its principle of solidification, can be divided into response type and closing
Type；Reaction type polyurethane hot-melt adhesive (PUR) is a kind of one pack system hot melt adhesive, is melted after heating, and flows scatter coated in substrate
Surface cools down after adherend bonding and forms excellent first adhesive property, then due to substrate surface contain micro-moisture or its
His compound containing active hydrogen reacts with isocyano (- NCO) and chemical crosslink reaction occurs, thus generate have it is highly cross-linked
A kind of structural bonding hot melt adhesive of network and cohesive force greatly.
Reaction type polyurethane hot-melt adhesive has technically obtained unprecedented development at present, mainly around high-adhesive-strength, eutectic
Body viscosity, open hour reprocess and the progress performances such as cured form are optimized and revised." reactive hot-melt is viscous disclosed in Chinese patent
Mixture ", application number are 201480080313.0, prepare it is a kind of with the removable polyurethane-hot melt adhesive reprocessed, more
It is suitable for high-end electronic product scope application." solvent-free damp solidifying polyurethane hotmelt combination disclosed in Chinese patent
Object ", application number are 201180047316.0, prepare it is a kind of low toxicity quickly establish adhesive property polyacrylate and polyester preparation
Polyurethane-hot melt viscose binder.In order to improve the cured form of Research of Moisture-curable Polyurethane Hot-melt Adhesive, " have disclosed in Chinese patent
Machine silicon modified polyurethane sealant ", application number is 2017102717258, prepares a kind of organic silicon modified polyurethane sealant,
Replace isocyano (- NCO) with silane coupling agent, is more suitable for applying under high humidity environment.Currently, reaction type polyurethane hot-melt adhesive
Research and development technology meets different type high-end electronic product scope application in fast development.Although reaction type polyurethane hot-melt adhesive energy
Highly cross-linked network is formed after hardening, but there is also the chemicals-resistant burn intos performances deficiency problem such as heat-resisting, fire-retardant.It is resistance to
Chemicals corrosive nature deficiency main cause is most of reaction type polyurethane hot-melt adhesives to improve its initial cohesiveness, be joined
A large amount of non-reacted thermoplasticity thickening resin or polynary acrylic copolymer.These non-reaction system thickening resins can not participate in
Solidification generates cross-linked network, to easily reduce the chemicals-resistant corrosive nature of polyurethane hot melt adhesive coating.
Summary of the invention
A kind of organic-silicon-modified reaction-type flame-retarding polyurethane is provided the purpose of the present invention is overcome the deficiencies in the prior art
Hot melt adhesive and preparation method thereof, since organic-silicon-modified reaction-type flame-retarding polyurethane hot melt introduces silane segment and response type resistance
Agent is fired, the chemicals-resistant corrosive nature of polyurethane coating, flame retardant property, heat resistance, ageing-resistant performance etc. can be further promoted.
In order to achieve the above object, the technical solution of organic-silicon-modified reaction-type flame-retarding polyurethane hot melt of the invention is
It is achieved, it is characterised in that including 1~20 part of polyether Glycols, 1~35 part of liquid polyesters dihydric alcohol, 1~40 part
Flame retardant polyether polyol, 1~35 part of crystalline polyester dihydric alcohol, 1~35 part contain isocyanate-modified poly-organosilicon third
Olefin(e) acid ester copolymer, 1~40 part of isocyanates, 0.01~1 part of catalyst, 0.01~1 part of antioxidant and 0.1~2 part
Silane coupling agent；It is above mass fraction；The chemistry containing isocyanate-modified poly-organosilicon acrylate copolymer
Structure is: it is poly- (methacryloxypropyl list block dimethyl polysiloxane-it is random-styrene-is random-methyl acrylate-
Randomly-isocyanatoethyl) i.e. P(MAPDMS-r-ST-r-MA-r-ICEMA), containing it is isocyanate-modified gather it is organic
The number-average molecular weight of Si acrylate copolymer is 1000~50000.
In the technical scheme, the polyether Glycols are polyoxypropyleneglycol of the number-average molecular weight 500~4000
One or two kinds of any combination of PPG or polytetrahydrofuran ether glycol PTMG；
The liquid polyesters dihydric alcohol be number-average molecular weight 200~2000 polyethylene glycol adipate glycol PEA, gather oneself two
Acid -1,6- hexylene glycol esterdiol PHA or polyadipate -1,4-butanediol esterdiol PMA one or more any combination；
The flame retardant polyether polyol is WANOL FR-130, the WANOL of Wanhua Chemical Group Co., Ltd.'s production
One or two kinds of any combination of FR-212 or WANOL FR-312；
The crystalline polyester dihydric alcohol is to win 7380 one or more of wound Degussa model 7320, model 7360 and model
Any combination；
The isocyanates is modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer)；
The catalyst is one or more kinds of any groups of triethanolamine, 2,2- dimorpholine base Anaesthetie Ether and phosphoric acid
It closes；
The antioxidant is one or both of 168 and 1010 any combination；
The silane coupling agent is anilinomethyl triethoxysilane ND-42.
In order to achieve the above object, the skill of organic-silicon-modified reaction-type flame-retarding polyurethane hot melt preparation method of the invention
Art scheme is achieved in that it is characterized in that preparation step is as follows:
Step 1 synthesis contains isocyanate-modified poly-organosilicon acrylate copolymer
1~35 part of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 1~40 part of styrene ST, 1
~40 parts of methyl acrylate MA and 1~10 part of isocyanatoethyl ICEMA is dissolved in 50~100 parts of toluene
In, 40~110 DEG C are controlled in, under nitrogen protection, 0.1~2 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added,
It polymerization reaction 2~50 hours, after rotary evaporation removes toluene, obtains and contains isocyanate-modified poly-organosilicon acrylic ester copolymer
Object, the number-average molecular weight containing isocyanate-modified poly-organosilicon acrylate copolymer are 1000~50000；Methacryloxypropyl
The number-average molecular weight that propyl list blocks dimethyl polysiloxane MAPDMS is 1000；
Step 2 synthesizing organo-silicon modified-reaction type flame retardant polyurethane hot melt adhesive
By 1~20 part of polyether Glycols, 1~35 part of liquid polyesters dihydric alcohol, 1~40 part of flame retardant polyether polyol, 1~
35 parts of crystalline polyester dihydric alcohol, 0.01~1 part of catalyst and 0.01~1 part antioxidant mixing after, calorify 120~
150 DEG C, vacuumize water removal about 1~3 hour, until mixture water content be lower than 280ppm, cool down in 70~100 DEG C,
Under nitrogen protection, be added 1~40 part isocyanates and 1~35 part contain isocyanate-modified poly-organosilicon acrylic ester copolymer
Object carries out polymerization reaction 1~10 hour, and sampling analysis polymerizate NCO% content reaches 1%~3%, and tested viscosity reaches at 100 DEG C
To 3000~15000 mPa.s, 0.1~2 part of silane coupling agent is added, obtains organic-silicon-modified reaction-type flame-retarding polyurethane heat
Melten gel is mass fraction above.
In the technical scheme, with Brookfield DV-C digital viscometer viscosity.
Compared with prior art, the present invention have following advantages and effects
It 1, is in the technical solution of the present invention, a kind of organosilicon list containing isocyanate-modified poly-organosilicon acrylate copolymer
Body, acrylic ester monomer and isocyanate function monomer are copolymerized.Organic silicon monomer can promote the solvent resistance of hot melt adhesive
Energy, heat resistance and ageing-resistant performance.Acrylic ester monomer can promote hot melt adhesive tack.Isocyanate function monomer can incite somebody to action
Containing isocyanate-modified poly-organosilicon acrylate copolymer subparticipation to base polyurethane prepolymer for use as synthetic reaction, response type is added
Fire retardant is formulated efficiently synergistic effect, shows preferable compatibility, and the other raw material compositions of a successive step of going forward side by side and content change
Kind chemicals-resistant corrosive nature and flame retardant property.
2, thickening resin acrylic copolymer random polycondensation is introduced base polyurethane prepolymer for use as by the present invention, improves thickening resin
With the compatibility of polyurethane, further the deficiencies of solving the problems, such as reaction type polyurethane hot-melt adhesive chemical resistance；
3, the present invention solves the problems, such as that traditional reaction type polyurethane hot-melt adhesive is poor to substrate wet performance, improves hot melt adhesive and applies
The flow leveling of glue, packaging and Process of Applying Glue are not likely to produce bubble.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Number involved in following embodiment is mass fraction.
Embodiment one
It is a kind of organic-silicon-modified reaction-type flame-retarding polyurethane hot melt, is prepared by the following steps to obtain:
Step 1 synthesis contains isocyanate-modified poly-organosilicon acrylate copolymer
By 13 parts of methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS, 25 parts of styrene ST, 10 parts
Methyl acrylate MA and 5 parts of isocyanatoethyl ICEMA are dissolved in 50 parts of toluene, are controlled in 90 DEG C,
Under nitrogen protection, 1.7 parts of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added, polymerization reaction 7 hours, rotary evaporation removed
It after removing toluene, obtains and contains isocyanate-modified poly-organosilicon acrylate copolymer, contain isocyanate-modified poly-organosilicon propylene
The number-average molecular weight of acid ester copolymer is 13000, and chemical structure is: poly- (it is poly- that methacryloxypropyl list blocks dimethyl
Siloxanes-is random-and styrene-is random-and methyl acrylate-is random-isocyanatoethyl) i.e. P(MAPDMS-r-ST-
R-MA-r-ICEMA)；The number-average molecular weight that methacryloxypropyl list blocks dimethyl polysiloxane MAPDMS is 1000,
No. CAS: 146632-07-7；
Step 2: synthesizing organo-silicon modified-reaction type flame retardant polyurethane hot melt adhesive
10 parts of polyoxypropyleneglycol PPG, 15 parts of polyethylene glycol adipate glycol PEA, 20 parts of flame retarding polyether is more
First alcohol WANOL FR-130,20 parts of 7320,0.1 parts of crystalline polyester dihydric alcohol of phosphoric acid and 0.2 part of irgasfos 168 are mixed
After conjunction, calorify 150 DEG C, vacuumize water removal 1 hour, until mixture water content be lower than 280ppm, cool down in 75 DEG C,
Under nitrogen protection, 20 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of modified diphenylmethane-is added) and
15 parts contain isocyanate-modified poly-organosilicon acrylate copolymer, carry out polymerization reaction 2 hours, sampling analysis polymerizate
NCO% content reaches 1.3%, and viscosity reaches 4800 mPa.s, 0.5 part of silane coupling agent ND-42 is added, obtains organosilicon and changes
Property reaction-type flame-retarding polyurethane hot melt, is mass fraction above；The number-average molecular weight of the polyoxypropyleneglycol PPG is
The number-average molecular weight of 1000, the polyethylene glycol adipate glycol PEA are 500, with Brookfield DV-C Digital Viscometer
Viscosity is measured, test temperature is set as 100 DEG C.
Embodiment two
It is a kind of organic-silicon-modified reaction-type flame-retarding polyurethane hot melt, is prepared by the following steps to obtain:
Step 1 synthesis contains isocyanate-modified poly-organosilicon acrylate copolymer
By 23 parts of methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS, 25 parts of styrene ST, 15 parts
Methyl acrylate MA and 6 parts of isocyanatoethyl ICEMA are dissolved in 70 parts of toluene, are controlled in 100 DEG C,
Under nitrogen protection, the thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester of 1.3 parts of addition, polymerization reaction 10 hours, rotary evaporation
It after removing toluene, obtains and contains isocyanate-modified poly-organosilicon acrylate copolymer, contain isocyanate-modified poly-organosilicon third
The number-average molecular weight of olefin(e) acid ester copolymer is 22000, and chemical structure is: poly- (methacryloxypropyl list blocks dimethyl
Polysiloxanes-is random-and styrene-is random-and methyl acrylate-is random-isocyanatoethyl) i.e. P(MAPDMS-r-
ST-r-MA-r-ICEMA)；Methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS number-average molecular weight be
1000, No. CAS: 146632-07-7；
Step 2 synthesizing organo-silicon modified-reaction type flame retardant polyurethane hot melt adhesive
By 5 parts of polytetrahydrofuran ether glycol PTMG, 20 parts of polyadipate -1,6- hexylene glycol esterdiol PHA, 25 parts fire-retardant
Polyether polyol WANOL FR-312,25 parts of 7360,0.4 parts of crystalline polyester dihydric alcohol of triethanolamine and 0.4 part it is anti-
After oxygen agent 168 mixes, 140 DEG C are calorified, vacuumizes water removal 2.5 hours, until the water content of mixture is lower than 280ppm, drop
Temperature is in 70 DEG C, under nitrogen protection, 25 parts of 4,4 '-diisocyanate Desmodur CD-C of modified diphenylmethane-is added
(MDI performed polymer) and 20 parts contain isocyanate-modified poly-organosilicon acrylate copolymer, carry out polymerization reaction 3 hours, take
Sample analysis polymerizate NCO% content reaches 2.0%, and viscosity reaches 5700 mPa.s, and 1.2 parts of silane coupling agent ND-42 is added,
Organic-silicon-modified reaction-type flame-retarding polyurethane hot melt is obtained, is above mass fraction；The polytetrahydrofuran ether glycol
The number-average molecular weight of PTMG is 2000, and the number-average molecular weight of polyadipate -1,6- hexylene glycol esterdiol PHA is 1000, is used
Brookfield DV-C digital viscometer viscosity, test temperature are set as 100 DEG C.
Embodiment three
It is a kind of organic-silicon-modified reaction-type flame-retarding polyurethane hot melt, is prepared by the following steps to obtain:
Step 1 synthesis contains isocyanate-modified poly-organosilicon acrylate copolymer
By 28 parts of methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS, 20 parts of styrene ST, 20 parts
Methyl acrylate MA and 8 parts of isocyanatoethyl ICEMA are dissolved in 80 parts of toluene, are controlled in 95 DEG C,
Under nitrogen protection, the thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester of 0.6 part of addition, polymerization reaction 10 hours, rotary evaporation
It after removing toluene, obtains and contains isocyanate-modified poly-organosilicon acrylate copolymer, contain isocyanate-modified poly-organosilicon third
The number-average molecular weight of olefin(e) acid ester copolymer is 32000, and chemical structure is: poly- (methacryloxypropyl list blocks dimethyl
Polysiloxanes-is random-and styrene-is random-and methyl acrylate-is random-isocyanatoethyl) i.e. P(MAPDMS-r-
ST-r-MA-r-ICEMA)；Methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS number-average molecular weight be
1000, No. CAS: 146632-07-7；
Step 2 synthesizing organo-silicon modified-reaction type flame retardant polyurethane hot melt adhesive
15 parts of polyoxypropyleneglycol PPG, 15 parts of polyethylene glycol adipate glycol PEA, 35 parts of flame retarding polyether is more
First alcohol WANOL FR-212,20 parts of 7360,0.2 parts of crystalline polyester dihydric alcohol of 2,2- dimorpholine base Anaesthetie Ether and
After 0.7 part of antioxidant 1010 mixing, 150 DEG C are calorified, water removal 3 hours is vacuumized, until the water content of mixture is lower than
280ppm cools down in 80 DEG C, under nitrogen protection, 35 parts of 4,4 '-diisocyanate of modified diphenylmethane-is added
Desmodur CD-C(MDI performed polymer) and 30 parts contain isocyanate-modified poly-organosilicon acrylate copolymer, polymerize
Reaction 7 hours, sampling analysis polymerizate NCO% content reach 2.5%, and viscosity reaches 6500 mPa.s, and 1.5 parts of silane is added
Coupling agent ND-42 obtains organic-silicon-modified reaction-type flame-retarding polyurethane hot melt, is above mass fraction；The polyoxygenated
The number-average molecular weight of propylene glycol PPG is 3000, and the number-average molecular weight of the polyethylene glycol adipate glycol PEA is 1500,
With Brookfield DV-C digital viscometer viscosity, test temperature is set as 100 DEG C.
Example IV
It is a kind of organic-silicon-modified reaction-type flame-retarding polyurethane hot melt, is prepared by the following steps to obtain:
Step 1 synthesis contains isocyanate-modified poly-organosilicon acrylate copolymer
By 33 parts of methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS, 10 parts of styrene ST, 25 parts
Methyl acrylate MA and 9 parts of isocyanatoethyl ICEMA are dissolved in 100 parts of toluene, are controlled in 100 DEG C,
Under nitrogen protection, the thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester of 0.3 part of addition, polymerization reaction 7 hours, rotary evaporation
It after removing toluene, obtains and contains isocyanate-modified poly-organosilicon acrylate copolymer, contain isocyanate-modified poly-organosilicon third
The number-average molecular weight of olefin(e) acid ester copolymer is 37000, and chemical structure is: poly- (methacryloxypropyl list blocks dimethyl
Polysiloxanes-is random-and styrene-is random-and methyl acrylate-is random-isocyanatoethyl) i.e. P(MAPDMS-r-
ST-r-MA-r-ICEMA)；Methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS number-average molecular weight be
1000, No. CAS: 146632-07-7；
Step 2 synthesizing organo-silicon modified-reaction type flame retardant polyurethane hot melt adhesive
By 20 parts of polyoxypropyleneglycol PPG, 30 parts of polyadipate -1,4-butanediol esterdiol PMA, 29 parts fire-retardant poly-
Ethoxylated polyhydric alcohol WANOL FR-312,15 parts of 7380,0.3 parts of crystalline polyester dihydric alcohol of triethanolamine and 0.6 part of antioxygen
Agent 168 mix after, calorify 150 DEG C, vacuumize water removal 2 hours, until mixture water content be lower than 280ppm, cooling in
90 DEG C, under nitrogen protection, it is pre- that 39 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI of modified diphenylmethane-is added
Aggressiveness) and the step of 35 parts one synthesis contain isocyanate-modified poly-organosilicon acrylate copolymer, it is small to carry out polymerization reaction 3
When, sampling analysis polymerizate NCO% content reaches 2.5%, and viscosity reaches 8200 mPa.s, and 0.9 part of silane coupling agent is added
ND-42 obtains organic-silicon-modified reaction-type flame-retarding polyurethane hot melt, is above mass fraction；The polypropylene oxide two
The number-average molecular weight of alcohol PPG is 4000, and the polyadipate -1,4-butanediol esterdiol PMA number-average molecular weight is 2000, is used
Brookfield DV-C digital viscometer viscosity, test temperature are set as 100 DEG C.
Performance test
The present invention hinders the organic-silicon-modified response type that the four kinds of above embodiments obtain referring to the universal method of current hot melt adhesive
Flame-retardant polyurethane hot melt adhesive carry out melt viscosity, the open hour, shore hardness, elongation at break, shear strength, oxygen index (OI) and with it is resistance to
Oleic acid testing performance index.Melt viscosity is tested referring to HG/T3660-1999 standard, selects No. 27 rotors, setting 100
℃.Open hour are tested referring to ASTM D4497-1994 (2004) method.Shore hardness is marked referring to GB-T2411-2008
Standard is tested.Elongation at break is tested referring to GB/T30776-2014 standard.Shear strength is referring to GB/T7124-2004
Standard is tested.Oxygen index (OI) is measured using GB/T5454-1997 " textile combustion performance test-oxygen index method ".Resistance toization
The specific test method of product performance indicator is that sample is prepared with reference to test shear strength method, and sample, which is placed 72 hours, solidifies it
Afterwards, sample is soaked in oleic acid (purity 98%) solution 24 hours, takes out sample, is placed in 85 DEG C and 85% relative humidity conditions
Under, after carrying out aging 1000 hours, then carry out shear strength test.Water contact angle is carried out with reference to GB/T 30693-2014 standard
Test.All test data comparative situations are see the following table 1.
Each embodiment specific performance of table 1 tests control case
It can be seen that the organic-silicon-modified reaction-type flame-retarding polyurethane hot melt of the invention synthesized with excellent from the data of table 1
Chemicals-resistant ageing properties and flame retardant property.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (3)
1. a kind of organic-silicon-modified reaction-type flame-retarding polyurethane hot melt, it is characterised in that including 1~20 part of polyether Glycols,
1~35 part of liquid polyesters dihydric alcohol, 1~40 part of flame retardant polyether polyol, 1~35 part of crystalline polyester dihydric alcohol, 1~
35 parts containing isocyanate-modified poly-organosilicon acrylate copolymer, 1~40 part of isocyanates, 0.01~1 part of catalysis
Agent, 0.01~1 part of antioxidant and 0.1~2 part of silane coupling agent；It is above mass fraction；It is described to change containing isocyanates
Property poly-organosilicon acrylate copolymer chemical structure be: it is poly- (methacryloxypropyl list block dimethyl polysiloxane-
Randomly-styrene-is random-and methyl acrylate-is random-isocyanatoethyl) i.e. P(MAPDMS-r-ST-r-MA-r-
ICEMA), the number-average molecular weight containing isocyanate-modified poly-organosilicon acrylate copolymer is 1000~50000.
2. organic-silicon-modified reaction-type flame-retarding polyurethane hot melt according to claim 1, it is characterised in that:
The polyether Glycols are polyoxypropyleneglycol PPG or polytetrahydrofuran ether two of the number-average molecular weight 500~4000
One or two kinds of any combination of alcohol PTMG；
The liquid polyesters dihydric alcohol be number-average molecular weight 200~2000 polyethylene glycol adipate glycol PEA, gather oneself two
Acid -1,6- hexylene glycol esterdiol PHA or polyadipate -1,4-butanediol esterdiol PMA one or more any combination；
The flame retardant polyether polyol is WANOL FR-130, the WANOL of Wanhua Chemical Group Co., Ltd.'s production
One or two kinds of any combination of FR-212 or WANOL FR-312；
The crystalline polyester dihydric alcohol is to win 7380 one or more of wound Degussa model 7320, model 7360 and model
Any combination；
The isocyanates is modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer)；
The catalyst is one or more kinds of any groups of triethanolamine, 2,2- dimorpholine base Anaesthetie Ether and phosphoric acid
It closes；
The antioxidant is one or both of 168 and 1010 any combination；
The silane coupling agent is anilinomethyl triethoxysilane ND-42.
3. a kind of organic-silicon-modified reaction-type flame-retarding polyurethane hot melt preparation method, it is characterised in that preparation step is as follows:
Step 1 synthesis contains isocyanate-modified poly-organosilicon acrylate copolymer
1~35 part of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 1~40 part of styrene ST, 1
~40 parts of methyl acrylate MA and 1~10 part of isocyanatoethyl ICEMA is dissolved in 50~100 parts of toluene
In, 40~110 DEG C are controlled in, under nitrogen protection, 0.1~2 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added,
It polymerization reaction 2~50 hours, after rotary evaporation removes toluene, obtains and contains isocyanate-modified poly-organosilicon acrylic ester copolymer
Object, the number-average molecular weight containing isocyanate-modified poly-organosilicon acrylate copolymer are 1000~50000；Methacryloxypropyl
The number-average molecular weight that propyl list blocks dimethyl polysiloxane MAPDMS is 1000；
Step 2 synthesizing organo-silicon modified-reaction type flame retardant polyurethane hot melt adhesive
By 1~20 part of polyether Glycols, 1~35 part of liquid polyesters dihydric alcohol, 1~40 part of flame retardant polyether polyol, 1~
35 parts of crystalline polyester dihydric alcohol, 0.01~1 part of catalyst and 0.01~1 part antioxidant mixing after, calorify 120~
150 DEG C, vacuumize water removal about 1~3 hour, until mixture water content be lower than 280ppm, cool down in 70~100 DEG C,
Under nitrogen protection, be added 1~40 part isocyanates and 1~35 part contain isocyanate-modified poly-organosilicon acrylic ester copolymer
Object carries out polymerization reaction 1~10 hour, and sampling analysis polymerizate NCO% content reaches 1%~3%, and tested viscosity reaches at 100 DEG C
To 3000~15000 mPa.s, 0.1~2 part of silane coupling agent is added, obtains organic-silicon-modified reaction-type flame-retarding polyurethane heat
Melten gel is mass fraction above.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708387A (en) * | 2020-12-25 | 2021-04-27 | 烟台德邦科技股份有限公司 | PFPE modified polyurethane single-component hot melt adhesive and preparation method thereof |
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|---|---|---|---|---|
| CN1845943A (en) * | 2003-06-09 | 2006-10-11 | 国家淀粉及化学投资控股公司 | Moisture curing reactive polyurethane hot melt adhesives modified with acrylic polymers |
| CN1901942A (en) * | 2003-12-30 | 2007-01-24 | 庄臣及庄臣视力保护公司 | Antimicrobial contact lenses and methods for their production |
| CN102504752A (en) * | 2011-11-30 | 2012-06-20 | 山东北方现代化学工业有限公司 | Room-temperature moisture-curable single-component flame-retardant polyurethane sealant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1845943A (en) * | 2003-06-09 | 2006-10-11 | 国家淀粉及化学投资控股公司 | Moisture curing reactive polyurethane hot melt adhesives modified with acrylic polymers |
| CN1901942A (en) * | 2003-12-30 | 2007-01-24 | 庄臣及庄臣视力保护公司 | Antimicrobial contact lenses and methods for their production |
| CN102504752A (en) * | 2011-11-30 | 2012-06-20 | 山东北方现代化学工业有限公司 | Room-temperature moisture-curable single-component flame-retardant polyurethane sealant |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112708387A (en) * | 2020-12-25 | 2021-04-27 | 烟台德邦科技股份有限公司 | PFPE modified polyurethane single-component hot melt adhesive and preparation method thereof |
| CN112708387B (en) * | 2020-12-25 | 2022-10-21 | 烟台德邦科技股份有限公司 | PFPE modified polyurethane single-component hot melt adhesive and preparation method thereof |
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Application publication date: 20190412 |