CN112251183A - Pressure-sensitive hot melt adhesive capable of being used at low temperature and preparation method thereof - Google Patents
Pressure-sensitive hot melt adhesive capable of being used at low temperature and preparation method thereof Download PDFInfo
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- CN112251183A CN112251183A CN202011055966.7A CN202011055966A CN112251183A CN 112251183 A CN112251183 A CN 112251183A CN 202011055966 A CN202011055966 A CN 202011055966A CN 112251183 A CN112251183 A CN 112251183A
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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
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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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6461—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having phosphorus
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
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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
- C08G2170/00—Compositions for adhesives
- C08G2170/40—Compositions for pressure-sensitive adhesives
Abstract
The invention belongs to the technical field of pressure-sensitive hot melt adhesives, and discloses a pressure-sensitive hot melt adhesive capable of being used at low temperature and a preparation method thereof. The pressure-sensitive hot melt adhesive capable of being used at low temperature is mainly prepared from the following components in parts by weight: 70-100 parts of a poly-phosphazene polyether polyol prepolymer and 2-5 parts of tackifying resin; the structure of the polyphosphazene polyether polyol prepolymer is shown in the formula I, and m and n are integers and are not 0. The method comprises the step of mixing a polyphosphazene-based polyether polyol prepolymer with tackifying resin to obtain the pressure-sensitive hot melt adhesive. The pressure-sensitive hot melt adhesive has good bonding property at low temperature and higher peel strength at-25 ℃.
Description
Technical Field
The invention belongs to the technical field of pressure-sensitive hot melt adhesives, and particularly relates to a pressure-sensitive hot melt adhesive capable of being used at a low temperature and a preparation method thereof.
Background
Pressure Sensitive Adhesives (PSAs) are a class of pressure sensitive adhesives. Generally, it is not used directly for bonding of an adherend, but it is made into a PSA article (tape or label) by various materials and then used for bonding of an adherend. The PSA has better initial adhesion, and can be bonded with an adherend with a smooth surface only by finger pressing; however, the peel strength of the PSA is not high and does not provide good adhesion in certain special applications. Moisture-curing PU-HMA (polyurethane hot melt adhesive) is a PU (polyurethane) adhesive containing end-NCO groups. When in use, the adhesive is heated and melted and then is applied with glue, after the glue layer is cooled (physically solidified) to generate primary bonding force, the terminal-NCO group in the glue layer reacts with moisture in the air or an active hydrogen compound on the surface of an adherend to generate chemical crosslinking solidification. The moisture-cured PU-HMA has very outstanding performance advantages, and a chemical crosslinking structure can be generated in the subsequent curing process, so that the moisture-cured PU-HMA has better heat resistance, water resistance and chemical medium resistance, and has wide application fields. However, when the polymer is used in certain low-temperature environments, the reactivity of the molecular functional group is insufficient due to low temperature, and the molecular chain movement is difficult at low temperature, so that the service performance (especially the bonding performance at low temperature) is greatly reduced, thereby limiting the further popularization and application of the polymer.
Disclosure of Invention
In order to overcome the defect that the existing pressure-sensitive adhesive has poor adhesive property in a low-temperature environment, the invention aims to provide a pressure-sensitive hot melt adhesive capable of being used at a low temperature and a preparation method thereof. The invention adopts the reaction of polyphosphazene and polyether polyol, and introduces the obtained polyphosphazene-based polyether polyol into the pressure-sensitive hot melt adhesive, so that the pressure-sensitive hot melt adhesive can have better adhesive property at lower temperature, and the application range of the pressure-sensitive adhesive is widened. The pressure-sensitive adhesive obtained by the invention can be used in an environment of-45 ℃.
The purpose of the invention is realized by the following technical scheme:
a pressure-sensitive hot melt adhesive capable of being used at low temperature is mainly prepared from the following components in parts by weight:
70-100 parts of poly-phosphorus nitrile polyether polyol prepolymer
And 2-5 parts of tackifying resin.
The structure of the polyphosphazene polyether polyol prepolymer is
m and n are integers and are not 0.
The polyphosphazene polyether polyol prepolymer is obtained by reacting polyphosphazene polyether polyol with 2, 4-TDI.
The structure of the poly-phosphorus nitrile-based polyether polyol is
m and n are integers and are not 0.
The preparation method of the polyphosphazene-based polyether polyol prepolymer comprises the following steps:
1) reacting polydichlorophosphazene with sodium p-methylphenoxide to obtain polyphosphazene containing p-methylphenoxy; oxidizing methyl in the polyphosphazene containing p-methylphenoxy into carboxyl in an oxidation system to obtain carboxyphenoxy polyphosphazene;
2) reacting carboxyphenoxyphosphazene with SOCl2Reacting to obtain acyl chloride phenoxy polyphosphazene;
3) reacting acyl chloride phenoxy polyphosphazene with oligomeric polyether polyamine to obtain polyphosphazene-based polyether polyol;
4) adding 2,4-TDI for reacting for 3-5 h to obtain the prepolymer.
The structure of the oligomeric polyether polyamine is
The molecular weight of the oligomeric polyether polyamine is 900-5000, and the molecular weight is the number average molecular weight.
The mol ratio of P to sodium P-hydroxyphenylphenolate in the polydichlorophosphazene in the step 1) is 1: (2-3). The reaction is carried out in an organic solvent. The organic solvent is THF.
The oxidation system is a 30% hydrogen peroxide and phosphotungstic acid system. The oxidation condition is that the reaction is carried out for 3-5 h at the temperature of 45-55 ℃.
Carboxyphenoxy polyphosphazene and SOCl in step 2)2The mass-to-volume ratio of (1) is 15 g: (200-400) mL. The reaction is carried out in an organic solvent; the reaction condition is that the reaction is carried out for 20-28 h at 65-75 ℃. After the reaction is finished, washing, filtering and drying are carried out in a protective atmosphere. The organic solvent is DMF. The washing is performed by using anhydrous THF.
The mass-volume ratio of the acyl chloride phenoxy polyphosphazene to the oligomeric polyether polyamine in the step 3) is 10g (200-400) mL, and preferably 10g (300 mL). The reaction condition is that the reaction is carried out for 6-8 h at 50-70 ℃. After the reaction, the product was washed and distilled under reduced pressure.
In the step 4), the poly-phosphorus nitrile polyether polyol and the 2,4-TDI meet the condition that the molar ratio of hydroxyl to isocyanate is 4: (1-2.5).
The oligomeric polyether polyamine is obtained by the following method:
a) in a solvent, adding NaN3Reacting with PECH (hydroxyl-terminated poly (epoxy chloropropane ether)) at 90-100 ℃ for 8-12 h, and performing subsequent treatment to obtain GAP (hydroxyl-terminated poly (azide glycidyl ether)); the solvent is [ Bmim ]]Cl-H2O mixed solvent with the mass ratio of 1: 1;
b) in an organic solvent, NaBH4Reacting with GAP (hydroxyl-terminated poly azide glycidyl ether) for 0.5-1.5 h under the condition of ice water bath, heating to 85-95 ℃, reacting for 7-9 h, and performing subsequent treatment to obtain the oligomeric polyether polyamine.
The NaN3With PECH (hydroxy terminated poly (chloropropylene oxide)) ether) The mol ratio of the medium Cl is (1-2): 1.
the subsequent treatment is washing with hot water, and reduced pressure distillation (reduced pressure distillation at 95-100 ℃ for 1-2 h).
NaBH in step b)4The mass ratio of the epoxy resin to GAP (hydroxyl-terminated polyazide glycidyl ether) is (7-8) g: 5g of the total weight. The organic solvent is methanol. The subsequent treatment is carried out with saturated NH4Cl adjusted the pH of the solution to 7-8 to quench NaBH4And filtered, then rotary distilled, CH2Cl2Extraction and filtration, rotary distillation.
The specific step of the step b) is to dissolve NaBH by adopting methanol at the temperature of 0-5 DEG C4And then, dropwise adding a GAP (hydroxyl-terminated polyazidine glycidyl ether) diluent obtained by diluting with methanol, stirring for 0.5-1.5 h, heating to 85-95 ℃, reacting for 7-9 h, and performing subsequent treatment to obtain the oligomeric polyether polyamine.
The preparation method of the pressure-sensitive hot melt adhesive capable of being used at low temperature comprises the following steps: and mixing the raw materials to obtain the pressure-sensitive adhesive.
The technological process of the polyphosphazene-based polyether polyol prepolymer comprises
Compared with the prior art, the invention has the following advantages and beneficial effects:
the pressure-sensitive hot melt adhesive has excellent bonding performance at low temperature.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
The preparation method of the poly-phosphazene polyether polyol prepolymer comprises the following steps:
(1) respectively taking equal mass of [ Bmim [ ]]Cl-H2Placing O mixed solvent in three-neck flask, placing PECH (average molecular weight 3000) in three-neck flask, heating to 95 deg.C in oil bath to mix well, adding excessive NaN3(NaN3The mol ratio of the product to Cl in PECH is 2:1), the temperature is kept constant at 95 ℃ (± 1 ℃), the reaction is carried out for 10 hours, hot deionized water is used for washing to remove salt in the mixed solution, and the reduced pressure distillation is carried out for 1 hour at the temperature of 98 ℃ to obtain GAP; 7.47g NaBH4Adding into a reaction container, placing into ice water mixed bath at 0-5 ℃, and slowly dropwise adding 150mL of anhydrous methanol to ensure that NaBH is added4Completely dissolving, slowly dropwise adding a GAP diluent (5g GAP is dissolved in 20mL of methanol), stirring for reaction for 1h, heating to room temperature, and transferring into a 90 ℃ oil bath pot for reflux reaction for 8 h; after the reaction is finished, saturated NH is used4Cl adjusted the pH of the solution to 7-8 to quench NaBH4Filtering, and rotary evaporating at 60 deg.C to remove methanol and THF, CH2Cl2Extracting, filtering, and rotary evaporating at 40 deg.C to remove CH as solvent2Cl2Obtaining an oligomeric polyether polyamine product 1 (with the molecular weight of 2600) for later use;
(2) under the protection of nitrogen, heating 10g of hexachlorocyclophosphazene, 35 ml of 1,2, 4-trichlorobenzene and 0.1 g of sulfamic acid to 170 ℃ for reacting for 4 hours, cooling to 60 ℃, pouring into n-heptane, and filtering to obtain a polydichlorophosphazene elastomer; dissolving an elastomer (poly (chlorophosphazene) in THF, adding excessive sodium methylphenolate (the specific dosage of the sodium methylphenolate is 2 times of the molar ratio of the poly (chlorophosphazene)) to react for 10 hours at normal temperature, and removing the THF by reduced pressure distillation to obtain a gray solid (the poly (phosphazene) containing p-methylphenoxy); the gray solid is put in a 30 percent hydrogen peroxide and phosphotungstic acid system (H)2O2The dosage of the phosphotungstic acid is 4 times of the molar weight of methyl in the polyphosphazene containing p-methylphenoxy, the dosage of the phosphotungstic acid is 0.1 to 0.3 times of the molar ratio of the polyphosphazene containing p-methylphenoxy), the mixture is heated to 50 ℃ to react for 4 hours, and the mixture is cooled to room temperature to obtain an off-white solid;
(3) 15g of the solid obtained above were weighed and 300ml of SOCl were added2Reacting with 5ml of mixed solution of sodium hydroxide and sodium hydroxide at 70 ℃ for 24 hours under stirring, cooling to room temperature, and reacting the reaction product in N2Wash-coat filter with anhydrous THF under protection until the solution is clear, and wash-coat with N2Drying and grinding the product in a drying oven to obtain black powdery solid acyl chloride phenoxy polyphosphazene;
(4) taking 10g of the black solid, adding 300ml of oligomeric polyether polyamine, stirring at 60 ℃ for reaction for 7h, and cooling to room temperature to obtain the polyphosphazene-based polyether polyol; adding 2,4-TDI for reacting for 4 hours, monitoring the content of NCO group in the reaction system to reach a theoretical value, finishing the reaction, and drying the product in vacuum for 6 hours to obtain the liquid-state poly-phosphorus nitrile-based polyether polyol prepolymer. The prepolymer prepared in this example had a viscosity (25 ℃ C.) of 3000 mPas.
Example 2
The preparation method of the poly-phosphazene polyether polyol prepolymer comprises the following steps:
(1) respectively taking equal mass of [ Bmim [ ]]Cl-H2Placing O mixed solvent in a three-neck flask, placing PECH (average molecular weight 4000) in the three-neck flask, heating to 95 deg.C in oil bath to mix them uniformly, adding excessive NaN3(NaN3The mol ratio of the product to Cl in PECH is 2:1), the temperature is kept constant at 95 ℃ (± 1 ℃), the reaction is carried out for 10 hours, hot deionized water is used for washing to remove salt in the mixed solution, and the reduced pressure distillation is carried out for 1 hour at the temperature of 98 ℃ to obtain GAP; 7.47g NaBH4Adding into a reaction container, placing into ice water mixed bath at 0-5 ℃, and slowly dropwise adding 150mL of anhydrous methanol to ensure that NaBH is added4Completely dissolving, slowly dropwise adding a GAP diluent (5g GAP is dissolved in 20mL of methanol), stirring for reaction for 1h, heating to room temperature, and transferring into a 90 ℃ oil bath pot for reflux reaction for 8 h; after the reaction is finished, saturated NH is used4Cl adjusted the pH of the solution to 7-8 to quench NaBH4Filtering, and rotary evaporating at 60 deg.C to remove methanol and THF, CH2Cl2Extracting, filtering, and rotary evaporating at 40 deg.C to remove CH as solvent2Cl2Obtaining oligomeric polyether polyamine (with the molecular weight of 3600) for later use;
(2) under the protection of nitrogen, heating 10g of hexachlorocyclophosphazene, 35 ml of 1,2, 4-trichlorobenzene and 0.1 g of sulfamic acid to 170 ℃ for reacting for 4 hours, cooling to 60 ℃, pouring into n-heptane, and filtering to obtain a polydichlorophosphazene elastomer; the elastomer (polydichlorophosphazene) is dissolved in THF, and an excess (sodium methylphenoxide is added specifically in an amount of polydichlorophosphazene moles2 times of the ratio) of sodium methylphenoxide, reacting for 10 hours at normal temperature, and distilling under reduced pressure to remove THF to obtain gray solid (polyphosphazene containing p-methylphenoxy); the gray solid is put in a 30 percent hydrogen peroxide and phosphotungstic acid system (H)2O2The dosage of the phosphotungstic acid is 4 times of the molar weight of methyl in the polyphosphazene containing p-methylphenoxy, the dosage of the phosphotungstic acid is 0.1 to 0.3 times of the molar ratio of the polyphosphazene containing p-methylphenoxy), the mixture is heated to 50 ℃ to react for 4 hours, and the mixture is cooled to room temperature to obtain an off-white solid;
(3) 15g of the solid obtained above were weighed and 300ml of SOCl were added2Reacting with 5ml of mixed solution of sodium hydroxide and sodium hydroxide at 70 ℃ for 24 hours under stirring, cooling to room temperature, and reacting the reaction product in N2Wash-coat filter with anhydrous THF under protection until the solution is clear, and wash-coat with N2Drying and grinding the product in a drying oven to obtain black powdery solid acyl chloride phenoxy polyphosphazene;
(4) taking 10g of the black solid, adding 300ml of oligomeric polyether polyamine, stirring at 60 ℃ for reaction for 7h, and cooling to room temperature to obtain the polyphosphazene-based polyether polyol; adding 2,4-TDI for reacting for 4 hours (the molar ratio of the hydroxyl group to the isocyanate is 2:1) to monitor the content of NCO group in the reaction system to reach a theoretical value, finishing the reaction, and vacuum drying the product for 6 hours to obtain the liquid-state poly (phosphorus nitrile group polyether polyol) prepolymer. The prepolymer prepared in this example had a viscosity (25 ℃ C.) of 4000 mPas.
Example 3
The preparation method of the poly-phosphazene polyether polyol prepolymer comprises the following steps:
(1) respectively taking equal mass of [ Bmim [ ]]Cl-H2Placing O mixed solvent in a three-neck flask, placing PECH (average molecular weight 5000) in the three-neck flask, heating to 95 deg.C in oil bath to mix them uniformly, adding excessive NaN3(NaN3The mol ratio of the product to Cl in PECH is 2:1), the temperature is kept constant at 95 ℃ (± 1 ℃), the reaction is carried out for 10 hours, hot deionized water is used for washing to remove salt in the mixed solution, and the reduced pressure distillation is carried out for 1 hour at the temperature of 98 ℃ to obtain GAP; 7.47g NaBH4Adding into a reaction container, placing into ice water mixed bath at 0-5 ℃, and slowly dropwise adding 150mL of anhydrous methanol to ensure that NaBH is added4The mixture is completely dissolved and dissolved in the solvent,then slowly dropwise adding a GAP diluent (5g GAP is dissolved in 20mL of methanol), stirring for reaction for 1h, raising the temperature to room temperature, and transferring the mixture into an oil bath kettle at the temperature of 90 ℃ for reflux reaction for 8 h; after the reaction is finished, saturated NH is used4Cl adjusted the pH of the solution to 7-8 to quench NaBH4Filtering, and rotary evaporating at 60 deg.C to remove methanol and THF, CH2Cl2Extracting, filtering, and rotary evaporating at 40 deg.C to remove CH as solvent2Cl2To obtain oligomeric polyether polyamine;
(2) under the protection of nitrogen, heating 10g of hexachlorocyclophosphazene, 35 ml of 1,2, 4-trichlorobenzene and 0.1 g of sulfamic acid to 170 ℃ for reacting for 4 hours, cooling to 60 ℃, pouring into n-heptane, and filtering to obtain a polydichlorophosphazene elastomer; dissolving an elastomer (poly (chlorophosphazene) in THF, adding excessive sodium methylphenolate (the dosage of the sodium methylphenolate is 2 times of the molar ratio of Cl in the poly (chlorophosphazene)) to react for 10 hours at normal temperature, and removing the THF by reduced pressure distillation to obtain a gray solid (the poly (phosphazene) containing p-methylphenoxy); the gray solid is put in a 30 percent hydrogen peroxide and phosphotungstic acid system (H)2O2The dosage of the phosphotungstic acid is 4 times of the molar weight of methyl in the polyphosphazene containing p-methylphenoxy, the dosage of the phosphotungstic acid is 0.1 to 0.3 times of the molar ratio of the polyphosphazene containing p-methylphenoxy), the mixture is heated to 50 ℃ to react for 4 hours, and the mixture is cooled to room temperature to obtain an off-white solid;
(3) 15g of the solid obtained above were weighed and 300ml of SOCl were added2Reacting with 5ml of mixed solution of sodium hydroxide and sodium hydroxide at 70 ℃ for 24 hours under stirring, cooling to room temperature, and reacting the reaction product in N2Wash-coat filter with anhydrous THF under protection until the solution is clear, and wash-coat with N2Drying and grinding the product in a drying oven to obtain black powdery solid acyl chloride phenoxy polyphosphazene;
(4) taking 10g of the black solid, adding 300ml of oligomeric polyether polyamine, stirring at 60 ℃ for reaction for 7h, and cooling to room temperature to obtain the polyphosphazene-based polyether polyol; adding 2,4-TDI for reacting for 4 hours (the molar ratio of the hydroxyl group to the isocyanate is 2:1) to monitor the content of NCO group in the reaction system to reach a theoretical value, finishing the reaction, and vacuum drying the product for 6 hours to obtain the liquid-state poly (phosphorus nitrile group polyether polyol) prepolymer. The prepolymer prepared in this example had a viscosity (25 ℃ C.) of 4000 mPas.
Example 4
A pressure-sensitive hot melt adhesive capable of being used at low temperature is prepared from the following components:
polyphosphazene polyether polyol prepolymer 80g
2.5g of tackifying resin.
The preparation method of the pressure-sensitive hot melt adhesive capable of being used at low temperature comprises the following steps: 80g of the polyacrylonitrile-based polyether polyol prepolymer (the prepolymer prepared in example 1) and 2.5g of the liquid rosin tackifying resin were stirred uniformly at 30 ℃ to obtain a pressure-sensitive adhesive as a dark brown solid.
Determination of the temperature peel strength of the pressure-sensitive adhesive prepared in this example: peel strength (-25 ℃, N/cm)-1) Is 3.4.
Example 5
A pressure-sensitive hot melt adhesive capable of being used at low temperature is prepared from the following components:
polyphosphazene polyether polyol prepolymer 80g
3g of tackifying resin.
The preparation method of the pressure-sensitive hot melt adhesive capable of being used at low temperature comprises the following steps: 80g of the polyacrylonitrile-based polyether polyol prepolymer (the prepolymer prepared in example 2) and 3g of the liquid rosin tackifying resin were uniformly stirred at 30 ℃ to obtain a pressure-sensitive adhesive which was a dark brown solid.
Measurement of low temperature peel strength of pressure-sensitive adhesive prepared in this example: peel strength (-25 ℃, N/cm)-1) Is 3.6.
Example 6
A pressure-sensitive hot melt adhesive capable of being used at low temperature is prepared from the following components:
polyphosphazene-based polyether polyol prepolymer (100 g)
2.5g of tackifying resin.
The preparation method of the pressure-sensitive hot melt adhesive capable of being used at low temperature comprises the following steps: 80g of the polyacrylonitrile-based polyether polyol prepolymer (the prepolymer prepared in example 3) and 2.5g of the liquid rosin tackifying resin were uniformly stirred at 30 ℃ to obtain the pressure-sensitive adhesive.
The pressure-sensitive adhesive prepared in this example was subjected to measurement of peel strength at low temperature: peel strength (-25 ℃, N/cm)-1) Was 4.2.
Claims (10)
1. The pressure-sensitive hot melt adhesive capable of being used at low temperature is characterized in that: the adhesive is mainly prepared from the following components in parts by weight:
70-100 parts of poly-phosphorus nitrile polyether polyol prepolymer
2-5 parts of tackifying resin;
the structure of the polyphosphazene polyether polyol prepolymer is shown as a formula I,
m and n are integers and are not 0.
2. The pressure-sensitive hot melt adhesive capable of being used at low temperature according to claim 1, wherein: the polyphosphazene polyether polyol prepolymer is obtained by reacting polyphosphazene polyether polyol with 2, 4-TDI;
the structure of the poly-phosphorus nitrile-based polyether polyol is
m and n are integers and are not 0.
3. The pressure-sensitive hot melt adhesive capable of being used at low temperature according to claim 2, wherein:
the preparation method of the polyphosphazene-based polyether polyol prepolymer comprises the following steps:
1) reacting polydichlorophosphazene with sodium p-methylphenoxide to obtain polyphosphazene containing p-methylphenoxy; oxidizing methyl in the polyphosphazene containing p-methylphenoxy into carboxyl in an oxidation system to obtain carboxyphenoxy polyphosphazene;
2) reacting carboxyphenoxyphosphazene with SOCl2Reacting to obtain acyl chloride phenoxy polyphosphazene;
3) reacting acyl chloride phenoxy polyphosphazene with oligomeric polyether polyamine to obtain polyphosphazene-based polyether polyol;
4) adding 2,4-TDI for reacting for 3-5 h to obtain a prepolymer;
the structure of the oligomeric polyether polyamine is
4. The pressure-sensitive hot melt adhesive capable of being used at low temperature according to claim 3, wherein: the molecular weight of the oligomeric polyether polyamine is 900-5000, and the molecular weight is the number average molecular weight.
5. The pressure-sensitive hot melt adhesive capable of being used at low temperature according to claim 3, wherein: the mol ratio of Cl to sodium p-hydroxyphenylate in the polydichlorophosphazene in the step 1) is 1: (1-2);
the oxidation system in the step 1) is a 30% hydrogen peroxide and phosphotungstic acid system;
carboxyphenoxy polyphosphazene and SOCl in step 2)2The mass-to-volume ratio of (1) is 15 g: (200-400) mL;
in the step 3), the mass-to-volume ratio of the acyl chloride phenoxy polyphosphazene to the oligomeric polyether polyamine is 10g (200-400) mL;
in the step 4), the poly-phosphorus nitrile polyether polyol and the 2,4-TDI meet the condition that the molar ratio of hydroxyl to isocyanate is 4: (1-2.5).
6. The pressure-sensitive hot melt adhesive capable of being used at low temperature according to claim 3, wherein: the oxidation condition in the step 1) is that the reaction is carried out for 3-5 h at the temperature of 45-55 ℃;
the reaction in step 1) is carried out in an organic solvent;
the reaction in the step 2) is carried out in an organic solvent; the reaction condition is that the reaction is carried out for 20-28 h at 65-75 ℃;
the reaction condition of the step 3) is that the reaction is carried out for 6-8 h at 50-70 ℃.
7. The pressure-sensitive hot melt adhesive capable of being used at low temperature according to claim 3, wherein:
the oligomeric polyether polyamine is obtained by the following method:
a) in a solvent, adding NaN3Reacting with PECH at 90-100 ℃ for 8-12 h, and performing subsequent treatment to obtain GAP (good GAP filler) terminal hydroxyl poly azide glycidyl ether;
b) in an organic solvent, NaBH4Reacting with GAP terminal hydroxyl poly-azide glycidyl ether for 0.5-1.5 h under the condition of ice water bath, heating to 85-95 ℃ for 7-9 h, and performing subsequent treatment to obtain the oligomeric polyether polyamine.
8. The pressure-sensitive hot melt adhesive capable of being used at low temperature according to claim 7, wherein: in step a) the solvent is [ Bmim ]]Cl-H2O mixed solvent with the mass ratio of 1: 1; the NaN in step a)3The mol ratio of the compound to Cl in PECH is (1-2): 1;
NaBH in step b)4The mass ratio of the obtained product to GAP is (7-8) g: 5g of the total weight.
9. The pressure-sensitive hot melt adhesive capable of being used at low temperature according to claim 7, wherein: the subsequent treatment in the step a) refers to washing with hot water and reduced pressure distillation;
the organic solvent in the step b) is methanol; the subsequent treatment in step b) is carried out with saturated NH4Cl adjusted the pH of the solution to 7-8 to quench NaBH4And filtered, then rotary distilled, CH2Cl2Extraction and filtration, rotary distillation.
10. The method for preparing a pressure-sensitive hot melt adhesive capable of being used at low temperature according to claim 1, wherein: the method comprises the following steps: and mixing the poly-phosphazene polyether polyol prepolymer with tackifying resin to obtain the pressure-sensitive adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011055966.7A CN112251183B (en) | 2020-09-29 | 2020-09-29 | Pressure-sensitive hot melt adhesive capable of being used at low temperature and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011055966.7A CN112251183B (en) | 2020-09-29 | 2020-09-29 | Pressure-sensitive hot melt adhesive capable of being used at low temperature and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112251183A true CN112251183A (en) | 2021-01-22 |
| CN112251183B CN112251183B (en) | 2022-04-12 |
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| CN112251183B (en) | 2022-04-12 |
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