CN109970888A - A kind of modified polyamide resin and preparation method thereof - Google Patents
A kind of modified polyamide resin and preparation method thereof Download PDFInfo
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- CN109970888A CN109970888A CN201910180121.1A CN201910180121A CN109970888A CN 109970888 A CN109970888 A CN 109970888A CN 201910180121 A CN201910180121 A CN 201910180121A CN 109970888 A CN109970888 A CN 109970888A
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- Prior art keywords
- polyamide resin
- modified polyamide
- acid
- nitrogen environment
- reaction kettle
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- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 32
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 26
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 26
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 14
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 13
- 239000001361 adipic acid Substances 0.000 claims abstract description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 12
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 12
- 239000011976 maleic acid Substances 0.000 claims abstract description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004952 Polyamide Substances 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 15
- 229920002647 polyamide Polymers 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 239000007848 Bronsted acid Substances 0.000 claims description 4
- 238000007171 acid catalysis Methods 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 150000007517 lewis acids Chemical class 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 abstract 1
- 230000002045 lasting effect Effects 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920006361 Polyflon Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a kind of modified polyamide resin, the reactant monomer including hexamethylene diamine, alcohol-soluble polyamide resin, methyl methacrylate, maleic acid, caprolactam, adipic acid and boronic acid monomer reacts obtained in reaction kettle nitrogen environment.The invention also discloses a kind of methods for preparing above-mentioned modified polyamide resin.Modified polyamide resin of the invention has heat resistance high, and more stable, color keep is lasting, and low temperature flow is good, the good advantage of absorption property.
Description
Technical field
The present invention relates to resin preparation fields, more specifically to a kind of modified polyamide resin and preparation method thereof.
Background technique
Modified polyamide resin is the widely used industrial chemicals of function admirable, can be divided by property non-reacted and neutral
Polyamide and reactive polyamide two major classes.Polyamide have strong tough and tensile, flexibility, binding force, wear-resisting, oil resistant, it is water-fast,
The features such as antienzyme bacterium, big water suction, neutral polyamide is mainly for the production of ink, heat sealer binder and coating, reactive polyamides
Amine is used for epoxy resin curing agent, thermosetting surface coating, binder, inner lining material and potting, moulded resin.
Currently, the research about modified polyamide resin emerges one after another.As disclosed in patent application 201680069138.4
High-fluidity polyamide resin combination, contains 50~99 mass % of (P) polyamide and (Q) meets following important documents (1)~(3)
1~50 mass % of acid modified polyolefin.(1) the melt flow rate (MFR) i.e. MFR measured under 230 DEG C, 2.16kg load is 50
~200g/10 minutes.(2) the modified amount of acid is 0.1~2.0 mass %.(3) containing elastomer based on maleic acid or its acid anhydrides
Modified body (q1), the elastomer contain 10~95 moles of % of the skeleton unit from ethylene, the skeleton unit 0 from propylene~
3~40 moles of % of skeleton unit of 80 moles of % and the alpha-olefin from carbon atom number 4~8, wherein the skeleton list from ethylene
The total amount of member, the skeleton unit from propylene and the skeleton unit from alpha-olefin is 100 moles of %.
A kind of for another example corrosion-resistant polyamide disclosed in patent application 201711472619.2 and preparation method thereof, it is described
Corrosion-resistant polyamide, including following raw material: polyamide, ABS resin, polyflon, epoxy acrylic
It is resin, propoxylated bisphenol, butadiene rubber, organic siliconresin, alkyd resin, dimethicone, polycarbonate, polylactic acid, different
Cyanate, methyl ethyl ketone peroxide, chlorinated paraffin, polyether acrylate, nano-aluminum hydroxide, polyphosphoric acids aluminium, hydroxy ethyl fiber
Element, zinc borate, zinc stearate, diatomite, silane coupling agent KH-560, corrosion-resistant modified additive, the corrosion-resistant polyamide
Resin be through preparation base-material, preparation modified materials, and will the materials such as base-material, modified materials mix and etc. made of.
Summary of the invention
To solve the above problems, the present invention adopts the following technical scheme that.
The present invention discloses a kind of modified polyamide resin, including hexamethylene diamine, alcohol-soluble polyamide resin, methyl-prop
E pioic acid methyl ester, maleic acid, caprolactam, adipic acid and organic boronic are 16~22:5~7:6~8:13 according to mass ratio
~16:8~11:23~27:4~7 are simultaneously made in reaction kettle nitrogen environment with the raw graft copolymerization of initiator hybrid concurrency.
Preferably: the weight of the initiator is the 0.5~0.75% of the weight of alcohol-soluble polyamide resin.
Invention additionally discloses a kind of methods for preparing above-mentioned modified polyamide resin, comprising the following steps:
Step 1: in reaction kettle nitrogen environment, 90 DEG C~140 DEG C, under the catalysis of tertiary amine or quaternary ammonium salt, to acyl in oneself
After amine, adipic acid carry out 0.5~1.5h of reaction, hydroxypolyamide is obtained；
Step 2: in reaction kettle nitrogen environment, 50 DEG C~80 DEG C, by hexamethylene diamine and organic boronic in Bronsted acid
Or it is reacted under lewis acidic catalysis；
Step 3: in reaction kettle nitrogen environment, by hydroxypolyamide obtained by reaction product in step 2 and step 1 and
Methyl methacrylate reacts 1~2h in organic solvent；
Step 4: 80~90 DEG C, initiator and alcohol-soluble polyamide resin are made into molten in reaction kettle nitrogen environment
Agent is slowly added dropwise in the reaction product of step 3, and time for adding is 1~1.5h, reaction；
Step 5: in reaction kettle nitrogen environment, 80 DEG C~130 DEG C, the p-methyl benzenesulfonic acid of quality 0.5wt%~4wt%
Or under sulfuric acid catalysis, by the product of step 4 with after maleic acid in organic solvent 1.5~3h of esterification, polyamides is obtained
Amine, then pH8.5~9.5 are neutralized to, add deionized water up to modified polyamide resin.
Preferably, the temperature of the step 1 is 120 DEG C.
Preferably, the reaction time is 1h in the step 1.
Preferably, the temperature in the step 2 is 70 DEG C.
Preferably, the temperature in the step 4 is 85 DEG C.
Preferably, the pH value in the step 5 is 9.
The present invention has the advantages that the present invention will be by that will include hexamethylene diamine, alcohol-soluble polyamide resin, methyl-prop
The various of monomer such as e pioic acid methyl ester, maleic acid, caprolactam, adipic acid and organic boronic in reaction kettle nitrogen environment with draw
The raw graft copolymerization of agent hybrid concurrency is sent out, functional modification polyamide is obtained.Hexamethylene diamine of the invention uses
Product can be made to keep original bright colors afterwards；Alcohol-soluble polyamide resin expires bonding force, weatherability, gelation, low-temperature stabilization
The requirement of property etc.；Alcohol-soluble is preferable, lighter color, transparency are high；Methyl methacrylate is soluble in ethyl alcohol, and property is stablized；
Hydrophilic on maleic acid strand, hydrophobic grouping present it is regular be alternately distributed, make it not only can be in hydrophilic system but also can be
It is used in oleophylic system；Caprolactam promotes polymerization；Adipic acid in the reaction, provides carbon skeleton；Carbon-carbon double bond, can be by polymerization point
Son connects together, and promotes polymerization, generates product.Modified polyamide resin of the invention has heat resistance height, more stable, color
It keeps persistently, low temperature flow is good, the good advantage of absorption property.
Specific embodiment
Below in conjunction in the embodiment of the present invention；Technical solution in the embodiment of the present invention is clearly and completely retouched
It states；Obviously；Described embodiments are only a part of the embodiments of the present invention；Instead of all the embodiments.Based on the present invention
In embodiment；Every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example；It shall fall within the protection scope of the present invention.
Embodiment 1
The present embodiment discloses a kind of modified polyamide resin, including hexamethylene diamine, alcohol-soluble polyamide resin, methyl
Methyl acrylate, maleic acid, caprolactam, adipic acid and organic boronic according to mass ratio be 16:5:6:13:8:23:4 simultaneously
It is made in reaction kettle nitrogen environment with the raw graft copolymerization of initiator hybrid concurrency.
The weight of the initiator is the 0.5% of the weight of alcohol-soluble polyamide resin.
Embodiment 2
The present embodiment discloses a kind of method for preparing 1 modified polyamide resin of embodiment, comprising the following steps:
Step 1: 90 DEG C, under the catalysis of tertiary ammonium salt, being carried out to caprolactam, adipic acid in reaction kettle nitrogen environment
After reacting 0.5h, hydroxypolyamide is obtained；
Step 2: in reaction kettle nitrogen environment, 50 DEG C, by hexamethylene diamine and organic boronic Bronsted acid catalysis
Lower reaction；
Step 3: in reaction kettle nitrogen environment, by hydroxypolyamide obtained by reaction product in step 2 and step 1 and
Methyl methacrylate reacts 1h in organic solvent；
Step 4: in reaction kettle nitrogen environment, 80 DEG C, by initiator dibenzoyl peroxide and alcohol-soluble polyamide resin
Rouge is made into solvent, is slowly added dropwise in the reaction product of step 3, time for adding 1h, reaction；
Step 5: in reaction kettle nitrogen environment, 80 DEG C, under Catalyzed by p-Toluenesulfonic Acid, by the product of step 4 and along fourth
Enedioic acid after esterification 1.5h, obtains polyamide, then be neutralized to pH8.5 in organic solvent, adds deionized water up to modified poly-
Amide resin.
The organic solvent that the present invention uses can be methylene chloride, and chloroform, benzene, nitrobenzene, carbon tetrachloride, butanone etc. are excellent
Selection of land methylene chloride.
Embodiment 3
The present embodiment discloses a kind of modified polyamide resin, including hexamethylene diamine, alcohol-soluble polyamide resin, methyl
Methyl acrylate, maleic acid, caprolactam, adipic acid and organic boronic are 22:7:8:16:11:27:7 according to mass ratio
And it is made in reaction kettle nitrogen environment with the raw graft copolymerization of initiator hybrid concurrency.
The weight of the initiator is the 0.75% of the weight of alcohol-soluble polyamide resin.
Embodiment 4
The present embodiment discloses a kind of method for preparing 3 modified polyamide resin of embodiment, comprising the following steps:
Step 1: in reaction kettle nitrogen environment, 140 DEG C, under the catalysis of quaternary ammonium salt, to caprolactam, adipic acid into
After row reaction 1.5h, hydroxypolyamide is obtained；
Step 2: 80 DEG C, hexamethylene diamine and organic boronic are urged lewis acidic in reaction kettle nitrogen environment
Change lower reaction；
Step 3: in reaction kettle nitrogen environment, by hydroxypolyamide obtained by reaction product in step 2 and step 1 and
Methyl methacrylate reacts 2h in organic solvent；
Step 4: in reaction kettle nitrogen environment, 90 DEG C, by initiator dibenzoyl peroxide and alcohol-soluble polyamide resin
Rouge is made into solvent, is slowly added dropwise in the reaction product of step 3, time for adding 1.5h, reaction；
Step 5: in reaction kettle nitrogen environment, 130 DEG C, under sulfuric acid catalysis, by the product and maleic acid of step 4
In organic solvent after esterification 3h, polyamide is obtained, then be neutralized to pH9.5, add deionized water up to modified polyamide resin.
Embodiment 5
The present embodiment discloses a kind of modified polyamide resin, including hexamethylene diamine, alcohol-soluble polyamide resin, methyl
Methyl acrylate, maleic acid, caprolactam, adipic acid and organic boronic are 20:6:7:14:10:25:6 according to mass ratio
And it is made in reaction kettle nitrogen environment with the raw graft copolymerization of initiator hybrid concurrency.
The weight of the initiator is the 0.6% of the weight of alcohol-soluble polyamide resin.
Embodiment 6
The present embodiment discloses a kind of method for preparing 5 modified polyamide resin of embodiment, comprising the following steps:
Step 1: in reaction kettle nitrogen environment, 120 DEG C, under the catalysis of quaternary ammonium salt, to caprolactam, adipic acid into
After row reaction 1h, hydroxypolyamide is obtained；
Step 2: in reaction kettle nitrogen environment, 70 DEG C, by hexamethylene diamine and organic boronic in Bronsted acid or Louis
It is reacted under the catalysis of this acid；
Step 3: in reaction kettle nitrogen environment, by hydroxypolyamide obtained by reaction product in step 2 and step 1 and
Methyl methacrylate reacts 1h in organic solvent；
Step 4: in reaction kettle nitrogen environment, 85 DEG C, by initiator dibenzoyl peroxide and alcohol-soluble polyamide resin
Rouge is made into solvent, is slowly added dropwise in the reaction product of step 3, time for adding 1h, reaction；
Step 5: in reaction kettle nitrogen environment, 100 DEG C, under Catalyzed by p-Toluenesulfonic Acid, by the product of step 4 and along fourth
Enedioic acid after 1.5~3h of esterification, obtains polyamide, then be neutralized to pH9 in organic solvent, adds deionized water up to modified poly-
Amide resin.
It is described above；It is merely preferred embodiments of the present invention；But scope of protection of the present invention is not limited thereto；
Anyone skilled in the art is in the technical scope disclosed by the present invention；According to the technique and scheme of the present invention and its
It improves design and is subject to equivalent substitution or change；It should be covered by the scope of protection of the present invention.
Claims (9)
1. a kind of modified polyamide resin, it is characterised in that: including hexamethylene diamine, alcohol-soluble polyamide resin, methyl-prop
E pioic acid methyl ester, maleic acid, caprolactam, adipic acid and organic boronic are 16~22:5~7:6~8:13 according to mass ratio
~16:8~11:23~27:4~7 are simultaneously made in reaction kettle nitrogen environment with the raw graft copolymerization of initiator hybrid concurrency.
2. modified polyamide resin according to claim 1, it is characterised in that: the weight of the initiator is that alcohol-soluble is poly-
The 0.5~0.75% of the weight of amide resin.
3. a kind of method prepared such as -2 described in any item modified polyamide resins according to claim 1, which is characterized in that packet
Include following steps:
Step 1: in reaction kettle nitrogen environment, 90 DEG C~140 DEG C, under the catalysis of tertiary amine or quaternary ammonium salt, to caprolactam,
After adipic acid carries out 0.5~1.5h of reaction, hydroxypolyamide is obtained；
Step 2: in reaction kettle nitrogen environment, 50 DEG C~80 DEG C, by hexamethylene diamine and organic boronic on Bronsted acid or road
It is reacted under the catalysis of Lewis acid；
Step 3: in reaction kettle nitrogen environment, by hydroxypolyamide obtained by reaction product in step 2 and step 1 and methyl
Methyl acrylate reacts 1~2h in organic solvent；
Step 4: 80~90 DEG C, initiator and alcohol-soluble polyamide resin are made into solvent in reaction kettle nitrogen environment, delay
Slowly it is added dropwise in the reaction product of step 3, time for adding is 1~1.5h, reaction；
Step 5: in reaction kettle nitrogen environment, 80 DEG C~130 DEG C, the p-methyl benzenesulfonic acid or sulphur of quality 0.5wt%~4wt%
Under acid catalysis, by the product of step 4 with after maleic acid in organic solvent 1.5~3h of esterification, polyamide is obtained, then
PH8.5~9.5 are neutralized to, add deionized water up to modified polyamide resin.
4. the method according to claim 3 for preparing modified polyamide resin, which is characterized in that the temperature of the step 1
It is 120 DEG C.
5. the method according to claim 4 for preparing modified polyamide resin, which is characterized in that reacted in the step 1
Time is 1h.
6. the method according to claim 4 for preparing modified polyamide resin, which is characterized in that the temperature in the step 2
Degree is 70 DEG C.
7. the method according to claim 4 for preparing modified polyamide resin, which is characterized in that the temperature in the step 4
Degree is 85 DEG C.
8. the method according to claim 4 for preparing modified polyamide resin, which is characterized in that the temperature in the step 5
Degree is 100 DEG C.
9. the method according to claim 4 for preparing modified polyamide resin, which is characterized in that the pH in the step 5
Value is 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116496681A (en) * | 2023-06-02 | 2023-07-28 | 珠海华夏奔腾化工有限公司 | Corrosion-resistant and wear-resistant modified polyamide resin coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613472A (en) * | 2009-06-30 | 2009-12-30 | 中国林业科学研究院林产化学工业研究所 | The preparation method of polyamide resin used for water color ink |
| CN108047387A (en) * | 2017-12-29 | 2018-05-18 | 天津华彩顺成装饰材料有限公司 | Modified polyamide resin and preparation method thereof and the water-based ink comprising the modified polyamide resin |
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2019
- 2019-03-11 CN CN201910180121.1A patent/CN109970888A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613472A (en) * | 2009-06-30 | 2009-12-30 | 中国林业科学研究院林产化学工业研究所 | The preparation method of polyamide resin used for water color ink |
| CN108047387A (en) * | 2017-12-29 | 2018-05-18 | 天津华彩顺成装饰材料有限公司 | Modified polyamide resin and preparation method thereof and the water-based ink comprising the modified polyamide resin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116496681A (en) * | 2023-06-02 | 2023-07-28 | 珠海华夏奔腾化工有限公司 | Corrosion-resistant and wear-resistant modified polyamide resin coating and preparation method thereof |
| CN116496681B (en) * | 2023-06-02 | 2024-03-29 | 珠海华夏奔腾化工有限公司 | Corrosion-resistant and wear-resistant modified polyamide resin coating and preparation method thereof |
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Application publication date: 20190705 |