CN107778978A - Environment-friendly type tin printing ink copolyesters and preparation method thereof - Google Patents
Environment-friendly type tin printing ink copolyesters and preparation method thereof Download PDFInfo
- Publication number
- CN107778978A CN107778978A CN201610747688.9A CN201610747688A CN107778978A CN 107778978 A CN107778978 A CN 107778978A CN 201610747688 A CN201610747688 A CN 201610747688A CN 107778978 A CN107778978 A CN 107778978A
- Authority
- CN
- China
- Prior art keywords
- copolyesters
- printing ink
- environment
- friendly type
- tin printing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D11/104—Polyesters
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
Abstract
The present invention relates to a kind of environment-friendly type tin printing ink copolyesters and preparation method thereof, the preparation method of the copolyesters mainly using ratio as（1.1~1.8）: 1.0 dihydric alcohol, dibasic carboxylic acid monomers are raw material, add catalyst and heat stabilizer, esterification is carried out under 200 DEG C~250 DEG C, 0~0.3MPa；After esterification terminates, the sodium sulfonate of ethylene isophthalate 5 or the sodium sulfonate of DMIP 5 are added under normal pressure, stirring ten minutes, it is less than 100Pa in pressure, polycondensation reaction is carried out at 260~280 DEG C of kettle temperature, discharging time is judged according to the change of power of agitator, finally gives the copolyesters of certain inherent viscosity.Polyester ink can be made with water, curing agent, filler, auxiliary agent in the copolyesters that the method for the invention is prepared by a certain percentage, and this tin printing ink greatly reduces organic solvent content, and have good adhesion property with Metal Substrate interface using water as main solvent.
Description
Technical field
The invention belongs to Polymer Synthesizing and application field, and in particular to a kind of environment-friendly type tin printing ink copolyesters and its
Preparation method.
Background technology
Mental package is used because of its good sealing and the bright-coloured pattern having in food, beverage, toy packaging, daily use chemicals
The industry such as product and household supplies is used widely.With the development of science and technology more and more products using polyester as raw material enter
Packaging field.Current ink industry often uses a large amount of organic solvents, and produced on-site worker and environment are caused to seriously endanger.Grind
Hair environment-friendly type tin printing ink is imperative, and tin printing ink copolyesters belongs to a kind of ease of solubility copolyesters, can be widely applied to oil
Black industry, there is resistance to medium, high tenacity, high adhesion force, meet the requirement of the deep processing processing of tin graphed sheet industry.
At present, tin printing ink copolyesters product is mainly by overseas enterprise's production and supply such as the spinning of Japanese Japan, South Korea SK, oil
Black manufacturing enterprise also increasingly pays close attention to domestic like product, on the one hand, can be with a certain degree of reduction production cost；The opposing party
Face, it can more be met the conjugated polyester resin of different product requirement.
Publication No. CN101781453A Chinese patent provide a kind of polyurethane dive curable ink resin and its
Preparation method, the preparation method point prepare polyester diol, prepare prepolymer, prepare the step of resin three.1. prepare polyester binary
Alcohol：Adipic acid, terephthalic acid (TPA), 1,3-BDO, 1,2-PD are added in synthesis reactor, heat up 200~240 DEG C of progress esters
Change reaction, react 5~6 hours, then to being vacuumized in synthesis reactor, obtain polyester diol.2. prepare prepolymer：It is made above-mentioned
Polyester diol and diisocyanate reacted 2~4 hours under the conditions of 90~110 DEG C, obtain isocyano-content for 5~
9% product is prepolymer.3. prepare resin：By organic solvent prepolymer under agitation it is uniform after, add more amine chainextenders, temperature
Control is at 70~80 DEG C.Reaction 2~3 hours, it is resin to obtain product.But application of the resin in ink and it is not inconsistent
The requirement that cyclization is protected.
The content of the invention
The mesh of the present invention is produced into reduce environmental hazard caused by tin printing ink industry, reduce ink industry
This, there is provided a kind of environment-friendly type tin printing ink copolyesters and preparation method thereof.
The present invention technical solution be：A kind of environment-friendly type tin printing ink is with copolyesters structural formula：
Wherein, R is dicarboxylic acids class monomer, and R ＇ are di-alcohols monomer；M=30~70, n=30~70, t=1~30.
Further, the dicarboxylic acids class monomer is terephthalic acid (TPA), M-phthalic acid, adipic acid, decanedioic acid and fourth
One kind in diacid.
Further, the di-alcohols monomer be ethylene glycol, neopentyl glycol, 1,4-CHDM, 2- methyl isophthalic acids,
One kind in ammediol.
Further, the intrinsic viscosity range of the copolyesters is 0.4~0.7dL/g, and molecular weight is 10000~16000,
Glass transition temperature is 40~60 DEG C, and acid number is less than 10mg KOH/g.
The preparation method of foregoing environment-friendly type tin printing ink copolyesters comprises the following steps：
(1) esterification：It is (1.1~1.8): 1.0 di-alcohols, two that molar ratio of alcohol to acid is added in polymerization reaction kettle
First carboxylic acid type monomer, adds catalyst and heat stabilizer, and esterification is carried out under 200 DEG C~250 DEG C, 0~0.3MPa, when
Between be 2~4 hours, esterification water yield when reaching theoretical value esterification complete；
(2) polycondensation reaction：At the end of esterification, system pressure is let out to normal pressure, adds M-phthalic acid ethylene glycol
Ester -5- sodium sulfonates or Sodium Dimethyl Isophthalate-5-sulfonate, stir ten minutes；Then, vacuum system is opened, by pressure drop
260~280 DEG C are risen to below 100Pa, while by reactor temperature, carries out polycondensation reaction；According to the change of power of agitator
Judge discharging time, finally give copolyesters.
Further, the dicarboxylic acids class monomer added in the polymerization reaction kettle is terephthalic acid (TPA), M-phthalic acid,
One or more in adipic acid, decanedioic acid and succinic acid；The di-alcohols monomer of addition is ethylene glycol, neopentyl glycol, 1,4-
One or more in cyclohexanedimethanol, 2- methyl-1,3-propanediols.
Further, the catalyst is antimony oxide, antimony acetate, antimony glycol, butyl titanate, ethylene glycol
Titanium, germanium system, zinc system or aluminum-based catalyst, addition are the 0.01%~0.1% of copolyesters gross mass.
Further, the heat stabilizer is phosphorus system heat stabilizer, addition for polyester gross mass 0.01%~
0.08%.
Yet further, the ethylene isophthalate -5- sodium sulfonates or Sodium Dimethyl Isophthalate-5-sulfonate
Addition accounts for the 1~15% of copolyesters gross mass.
The substantive distinguishing features of the protrusion of technical solution of the present invention and significant progress are mainly reflected in：
1st, environment-friendly type tin printing ink copolyesters of the present invention, is linear straight chain structure, is not crosslinked, and is not added any
The polyfunctional monomers such as trifunctional, four-functional group, belong to a kind of water-soluble copolyester, can be with water, curing agent, filler, auxiliary agent
Deng polyester ink is made by a certain percentage.
When the 2nd, preparing tin printing ink using copolyesters of the present invention, using water as main solvent, cosolvent (organic solvent)
Content is less than 10%, consumption of organic solvent is significantly reduced, so as to reduce organic compound (VOC) discharge；It is and made
The ink obtained has good adhesive property with metal primary surface, has the characteristics that resistance to medium, high tenacity, high adhesion force, can expire
The requirement of footmark ink rail industry deep processing processing.
3rd, the preparation method of environment-friendly type tin printing ink copolyesters of the present invention, technique is simple, and anti-in a polymerization
Answering in kettle to complete, and cost is relatively low, be easy to industrialized production.
Embodiment
The present invention relates to a kind of environment-friendly type tin printing ink copolyesters, its structural formula is：
Wherein, R is dicarboxylic acids class monomer, is terephthalic acid (TPA), M-phthalic acid, adipic acid, decanedioic acid and succinic acid
In one kind, R ＇ are di-alcohols monomer, are ethylene glycol, neopentyl glycol, 1,4-CHDM, 2- methyl isophthalic acids, 3- the third two
One kind in alcohol, m=30~70, n=30~70, t=1~30.The intrinsic viscosity range of the copolyesters is 0.4~0.7dL/
G, molecular weight are 10000~16000, and glass transition temperature is 40~60 DEG C, and acid number is less than 10mg KOH/g.
The preparation method step of above-mentioned copolyesters is as follows：
(1) esterification：
Molar ratio of alcohol to acid (1.1~1.8): 1.0 di-alcohols, dicarboxylic acids class monomer is added in polymerization reaction kettle,
Certain proportion catalyst and heat stabilizer are added, carries out esterification under 200 DEG C~250 DEG C, 0~0.3MPa, the time is 2~
4 hours, esterification was completed when esterification water yield reaches theoretical value.Wherein, the catalyst charge is copolyesters gross mass
0.01%~0.1%；The addition of the heat stabilizer is the 0.01%~0.08% of polyester gross mass.
Wherein, the dicarboxylic acids class monomer of addition is terephthalic acid (TPA), M-phthalic acid, adipic acid, decanedioic acid and fourth two
One or more in acid；Di-alcohols monomer is ethylene glycol, neopentyl glycol, 1,4 cyclohexane dimethanol, 2- methyl isophthalic acids, 3- third
One or more in glycol；The catalyst is antimony oxide, antimony acetate, antimony glycol, butyl titanate, ethylene glycol
Titanium, germanium system, zinc system, aluminum-based catalyst etc.；Described heat stabilizer uses phosphorus system heat stabilizer.
(2) polycondensation reaction：
When esterification water yield reaches theoretical value, esterification terminates, and system pressure is let out to normal pressure, adds certain proportion
Ethylene isophthalate -5- sodium sulfonates (SIPE) or Sodium Dimethyl Isophthalate-5-sulfonate (SIPM), stirring very
Clock, vacuum system is opened, pressure is down to below 100Pa, while by temperature rise in reactor to 260~280 DEG C, on this condition
Polycondensation reaction is carried out, discharging time is judged according to the change of power of agitator, finally gives the copolyesters of certain inherent viscosity.It is described
SIPE (or SIPM) addition accounts for the 1~15% of copolyesters gross mass.
Foregoing copolyesters mixes and can be prepared by polyester ink by a certain percentage with water, curing agent, filler, auxiliary agent.It is resulting
Tin printing ink be a kind of environment-friendlyink ink, using water as main solvent, cosolvent (organic solvent) content be less than 10%, greatly
Consumption of organic solvent is reduced, reduces VOC (VOC) discharge；And ink has good glue with metal primary surface
Tie performance.
Technical solution of the present invention is specifically illustrated below in conjunction with specific embodiment, but this is the excellent of the present invention
Select embodiment, it is noted that for those skilled in the art, do not departing from the technology of the present invention principle
Under the premise of, some improvement and modification can also be made, these improvement and modification should also be considered as protection scope of the present invention it
It is interior.
Embodiment one：In 20 liters of polymerization reaction kettles, p-phthalic acid, isophthalic are added by the ︰ 1.0 of molar ratio of alcohol to acid 1.5
Dioctyl phthalate, adipic acid and ethylene glycol, neopentyl glycol, 1,4 cyclohexane dimethanol.Wherein, dicarboxylic acids shared by p-phthalic acid
The ratio of total moles is 65%, and the ratio of dicarboxylic acids total moles shared by M-phthalic acid is 25%, binary carboxylic shared by adipic acid
The ratio of sour total moles is 10%；The ratio of dihydric alcohol total moles shared by ethylene glycol is 74%, and dihydric alcohol shared by neopentyl glycol is total
Mole ratio be 20%, dihydric alcohol total moles ratio shared by 1,4-CHDM be 6%, add 2g antimony glycols.Nitrogen
Gas is replaced, heating, and esterification is carried out under 200 DEG C~250 DEG C, 0.0~0.3MPa, when esterification water yield reaches theoretical value,
Esterification Stage terminates.Let out to normal pressure, add 1g trimethyl phosphates as stabilizer, adding SIPE, (addition is copolyesters quality
15%), stir ten minutes, open vacuum system, into polycondensation reaction.Polycondensation reaction stage, pressure are less than 100Pa, reaction
Temperature control system is at 260~280 DEG C in kettle.Discharging time is judged according to the change of power of agitator, finally give inherent viscosity for 0.4~
0.7dL/g copolyesters.
Embodiment two：Using the addition with the identical raw material proportioning of embodiment one and catalyst loading, only adjustment SIPE
Measure as the 8% of copolyesters quality, aggregation test is carried out under the process conditions of embodiment one, obtains the copolymerization of certain inherent viscosity
Ester.
Embodiment three：In 20 liters of polymerization reaction kettles, terephthalic acid (TPA), isophthalic two are added by the ︰ 1.0 of molar ratio of alcohol to acid 1.2
Formic acid, succinic acid and ethylene glycol, neopentyl glycol, 2- methyl-1,3-propanediols, 1,4 cyclohexane dimethanol.Wherein, essence is to benzene two
The ratio of dicarboxylic acids total moles shared by formic acid is 60%, and the ratio of dicarboxylic acids total moles shared by M-phthalic acid is 20%,
The ratio of dicarboxylic acids total moles shared by succinic acid is 20%；The ratio of dihydric alcohol total moles shared by ethylene glycol is 60%, new penta
The ratio of dihydric alcohol total moles shared by glycol is 20%, 2- methyl isophthalic acids, and the ratio of dihydric alcohol total moles is shared by ammediol
10%, the ratio of dihydric alcohol total moles shared by 1,4-CHDM is 10%；1.5g antimony oxides are added as catalysis
Agent, nitrogen displacement, heating carry out esterification under 200 DEG C~250 DEG C, 0.0~0.3MPa, and esterification water yield reaches theoretical
During value, Esterification Stage terminates.Let out to normal pressure, add the phosphoric acid solution 36g that mass concentration is 2%, adding SIPM, (addition is common
Polyester quality 6%), stir ten minutes.It is polymerize using with the identical polymerization technique of embodiment one, obtaining inherent viscosity is
0.4~0.7dL/g copolyesters.
Example IV：In 20 liters of polymerization reaction kettles, the ︰ 1.0 of molar ratio of alcohol to acid 1.7 terephthalic acid (TPA), isophthalic two are added
Formic acid and ethylene glycol, 2- methyl-1,3-propanediols, 1,4 cyclohexane dimethanol.Wherein, binary acid shared by terephthalic acid (TPA) always rubs
Your ratio is 60%, and the ratio of binary acid total moles shared by M-phthalic acid is 40%；Dihydric alcohol total moles shared by ethylene glycol
Ratio is 70%, 2- methyl isophthalic acids, and the ratio of dihydric alcohol total moles shared by 3 propane diols is 15%, shared by 1,4-CHDM
The ratio of dihydric alcohol total moles is 15%；Add 1g butyl titanates be used as catalyst, nitrogen displacement, heat up, 200 DEG C~
250 DEG C, esterification is carried out under 0.0~0.3MPa, when esterification water yield reaches theoretical value, Esterification Stage terminates.Let out to normal pressure,
1.5g trimethyl phosphates are added as stabilizer, SIPM (addition is the 10% of copolyesters quality) is added, stirs ten minutes.Adopt
It is polymerize with the identical polymerization technique of embodiment one, obtains the copolyesters that inherent viscosity is 0.4~0.7dL/g.
Embodiment five：In 150 liters of polymerization reaction kettles, the ︰ 1.0 of molar ratio of alcohol to acid 1.4 p-phthalic acid, isophthalic are added
Dioctyl phthalate and ethylene glycol, neopentyl glycol, 2- methyl-1,3-propanediols, 1,4 cyclohexane dimethanol.Wherein shared by terephthalic acid (TPA)
The ratio of dicarboxylic acids total moles is 55%, to account for the ratios of dicarboxylic acids total moles be 45% to M-phthalic acid；Wherein ethylene glycol
The ratio of shared dihydric alcohol total moles is 18%, 2- methyl isophthalic acids, and the ratio that ammediol accounts for dihydric alcohol total moles is 55%, Isosorbide-5-Nitrae-
The ratio of dihydric alcohol total moles shared by cyclohexanedimethanol is 27%.16.5g germanium dioxides are added as catalyst.By above-mentioned list
After body addition system, nitrogen displacement, heating, esterification is carried out under 200 DEG C~250 DEG C, 0.0~0.3MPa, be esterified water outlet
When amount reaches theoretical value, reach esterification terminal.Let out to normal pressure, add 5g phosphoric acid as stabilizer, adding SIPE, (addition is common
Polyester quality 10%), stir 10 minutes.It is polymerize using with the identical polymerization technique of embodiment one, obtains inherent viscosity
For 0.4~0.7dL/g copolyesters.
Claims (12)
- A kind of 1. environment-friendly type tin printing ink copolyesters, it is characterised in that：The structural formula of the copolyesters is：Wherein, R is dicarboxylic acids class monomer, and R ＇ are di-alcohols monomer；M=30~70, n=30~70, t=1~30.
- 2. environment-friendly type tin printing ink copolyesters according to claim 1, it is characterised in that：The dicarboxylic acids class monomer For one kind in terephthalic acid (TPA), M-phthalic acid, adipic acid, decanedioic acid and succinic acid.
- 3. environment-friendly type tin printing ink copolyesters according to claim 1, it is characterised in that：The di-alcohols monomer is One kind in ethylene glycol, neopentyl glycol, 1,4 cyclohexane dimethanol, 2- methyl-1,3-propanediols.
- 4. environment-friendly type tin printing ink copolyesters according to claim 1, it is characterised in that：The characteristic of the copolyesters is glued Degree scope is 0.4~0.7dL/g, and molecular weight is 10000~16000, and glass transition temperature is 40~60 DEG C, and acid number is less than 10mg KOH/g。
- 5. the preparation method of the environment-friendly type tin printing ink copolyesters described in claim 1, it is characterised in that：This method include with Lower step,(1) esterification：It is (1.1~1.8) that molar ratio of alcohol to acid is added in polymerization reaction kettle: 1.0 di-alcohols, binary carboxylic Acrylic monomer, catalyst and heat stabilizer are added, esterification is carried out under 200 DEG C~250 DEG C, 0~0.3MPa, the time is 2~4 hours, esterification was completed when esterification water yield reaches theoretical value；(2) polycondensation reaction：At the end of esterification, system pressure is let out to normal pressure, adds ethylene isophthalate -5- Sodium sulfonate or Sodium Dimethyl Isophthalate-5-sulfonate, stir ten minutes；Then, vacuum system is opened, pressure is down to Below 100Pa, while reactor temperature is risen to 260~280 DEG C, carry out polycondensation reaction；Sentenced according to the change of power of agitator Disconnected discharging time, finally gives copolyesters.
- 6. the preparation method of environment-friendly type tin printing ink copolyesters according to claim 5, it is characterised in that：The polymerization The dicarboxylic acids class monomer added in reactor is in terephthalic acid (TPA), M-phthalic acid, adipic acid, decanedioic acid and succinic acid It is one or more.
- 7. the preparation method of environment-friendly type tin printing ink copolyesters according to claim 5, it is characterised in that：The polymerization The di-alcohols monomer added in reactor is ethylene glycol, neopentyl glycol, 1,4 cyclohexane dimethanol, 2- methyl isophthalic acids, 3- the third two One or more in alcohol.
- 8. the preparation method of environment-friendly type tin printing ink copolyesters according to claim 5, it is characterised in that：The catalysis Agent is antimony oxide, antimony acetate, antimony glycol, butyl titanate, titanium ethylene glycolate, germanium system, zinc system or aluminum-based catalyst.
- 9. the preparation method of environment-friendly type tin printing ink copolyesters according to claim 5, it is characterised in that：The heat is steady It is phosphorus system heat stabilizer to determine agent.
- 10. the preparation method of environment-friendly type tin printing ink copolyesters according to claim 8, it is characterised in that：It is described to urge Agent addition is the 0.01%~0.1% of copolyesters gross mass.
- 11. the preparation method of environment-friendly type tin printing ink copolyesters according to claim 9, it is characterised in that：The heat The addition of stabilizer is the 0.01%~0.08% of polyester gross mass.
- 12. the preparation method of tin printing ink copolyesters according to claim 5, it is characterised in that：The isophthalic diformazan Sour glycol ester -5- sodium sulfonates or Sodium Dimethyl Isophthalate-5-sulfonate addition account for the 1~15% of copolyesters gross mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610747688.9A CN107778978A (en) | 2016-08-26 | 2016-08-26 | Environment-friendly type tin printing ink copolyesters and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610747688.9A CN107778978A (en) | 2016-08-26 | 2016-08-26 | Environment-friendly type tin printing ink copolyesters and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107778978A true CN107778978A (en) | 2018-03-09 |
Family
ID=61441585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610747688.9A Pending CN107778978A (en) | 2016-08-26 | 2016-08-26 | Environment-friendly type tin printing ink copolyesters and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107778978A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117447687A (en) * | 2023-12-21 | 2024-01-26 | 河南源宏高分子新材料有限公司 | Low-warpage high-viscosity PETG copolyester and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079812A (en) * | 2010-11-16 | 2011-06-01 | 苏州瀚海化学有限公司 | Water-soluble copolyester and preparation method thereof |
| CN102558527A (en) * | 2011-12-19 | 2012-07-11 | 东华大学 | Method for preparing water-soluble polyester based on aluminum compound as catalyst |
| CN102757552A (en) * | 2012-07-19 | 2012-10-31 | 苏州瀚海化学有限公司 | Water-soluble copolyester and preparation method thereof |
| CN105579527A (en) * | 2013-12-17 | 2016-05-11 | 尤尼吉可株式会社 | Polyester resin composition, and molding obtained using same |
-
2016
- 2016-08-26 CN CN201610747688.9A patent/CN107778978A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079812A (en) * | 2010-11-16 | 2011-06-01 | 苏州瀚海化学有限公司 | Water-soluble copolyester and preparation method thereof |
| CN102558527A (en) * | 2011-12-19 | 2012-07-11 | 东华大学 | Method for preparing water-soluble polyester based on aluminum compound as catalyst |
| CN102757552A (en) * | 2012-07-19 | 2012-10-31 | 苏州瀚海化学有限公司 | Water-soluble copolyester and preparation method thereof |
| CN105579527A (en) * | 2013-12-17 | 2016-05-11 | 尤尼吉可株式会社 | Polyester resin composition, and molding obtained using same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117447687A (en) * | 2023-12-21 | 2024-01-26 | 河南源宏高分子新材料有限公司 | Low-warpage high-viscosity PETG copolyester and preparation method thereof |
| CN117447687B (en) * | 2023-12-21 | 2024-03-08 | 河南源宏高分子新材料有限公司 | Low-warpage high-viscosity PETG copolyester and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2510411C2 (en) | Two-component solvent-free polyurethane adhesive with low content of free mdi monomer | |
| JP5184739B2 (en) | Process for producing isosorbide-containing polyester | |
| JP5370994B2 (en) | Soluble copolyester resin | |
| CN104449531B (en) | A kind of metal packaging tank dual-component polyurethane resin and preparation method thereof | |
| CN106565965A (en) | Hyperbranched hydroxyl polyester resin, and preparation method and application of hyperbranched hydroxyl polyester resin | |
| CN104448272B (en) | A kind of aromatic series high flame retardant PEPA and its production and use | |
| EP2013260B1 (en) | Process for the preparation of polyesters containing 1,4-cyclohexanedimethanol | |
| CN111072941A (en) | Method for synthesizing linear and polyfunctional polyester polyol from diepoxide | |
| CN101126006A (en) | Method for preparing polyester thermosol | |
| CN102276808A (en) | Preparation method of polyterephthalic acid ethane diacid glycol copolyester | |
| JP2019536830A (en) | Polyphenol alkoxylates and coatings including blends | |
| CN112143437A (en) | Lithium battery aluminum plastic film outer layer adhesive resin and preparation and application thereof | |
| CN104497283A (en) | Mixed acid type polyester polyol and preparation method thereof | |
| CN106432703A (en) | Hydroxyl polyester resin with high solid content and preparation method and application thereof | |
| CN102276806A (en) | Preparation method of polyterephthalic acid ethane diacid butanediol copolyester | |
| CN107892744A (en) | A kind of preparation method of Heat Shrinkage Film Polyester section | |
| EP3875514A1 (en) | Copolyester resin, molded product, and heat-shrinkable film | |
| CN107163234A (en) | A kind of powdery paints bio-based polyester resin and preparation method thereof | |
| JP2018193537A (en) | Polyester-based adhesive and its adhesive sheet | |
| CN107778978A (en) | Environment-friendly type tin printing ink copolyesters and preparation method thereof | |
| CN102276807A (en) | Method for preparing polyethylene terephthalate copolyester | |
| CN101508771A (en) | Method of preparing biodegradable multicomponent copolyester | |
| CN109232867A (en) | A kind of aqueous copolyesters and preparation method thereof | |
| JP5970866B2 (en) | Biomass plastic paint | |
| CN102453238A (en) | Preparation method of biodegradable polyester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180309 |
|
| RJ01 | Rejection of invention patent application after publication |