CN108129643A - A kind of terminal carboxyl polyester resin and preparation method thereof - Google Patents
A kind of terminal carboxyl polyester resin and preparation method thereof Download PDFInfo
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- CN108129643A CN108129643A CN201711406643.6A CN201711406643A CN108129643A CN 108129643 A CN108129643 A CN 108129643A CN 201711406643 A CN201711406643 A CN 201711406643A CN 108129643 A CN108129643 A CN 108129643A
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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
- 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
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a kind of terminal carboxyl polyester resins and preparation method thereof.Polyester resin feed stock component and its mass parts are：3.6 4.1 parts of alcohol, 6.3 6.8 parts of acid, 0.01 part of esterification catalyst, 0.2 0.6 parts of bion succinic acid, 0.004 0.005 parts of curing accelerator.The present invention prepares polyester resin using bion raw material, ensures good comprehensive performance while reducing industry carbon emission.
Description
Technical field
The invention belongs to technical field of coatings, and in particular to a kind of terminal carboxyl polyester resin and preparation method thereof.
Background technology
With the fast development of powdery paints, the demand of polyester resin is continuously increased.Produce the primary raw material of polyester resin
It is from petrochemical industry route that such as terephthalic acid (TPA), adipic acid, neopentyl glycol are mostly, and the consumption of these raw materials means largely can not
Regenerate the disappearance of petroleum resources.Therefore, development and application bion raw material are a directions of PET industry sustainable development.Amber
Amber acid is a kind of common natural organic acids, widely used, and the biology for being considered following most worthy by U.S. Department of Energy refines
One of product processed.As important Organic Chemicals and synthetic intermediate, succinic acid can be produced by biological fermentation process, which can
Greenhouse gas emission is reduced, it is environmentally protective, it is energy saving.Therefore, bion succinic acid is used for polyester resin for powder coating
Synthesis in, can effectively reduce the carbon emission of entire industry, meet the theory of sustainable development.
Invention content
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of terminal carboxyl polyester resin and its preparation sides
Method.The present invention prepares polyester resin using bion raw material, ensures good comprehensive performance while reducing industry carbon emission.
The technical solution adopted by the present invention is：
A kind of terminal carboxyl polyester resin, raw material components and its mass parts are：3.6-4.1 parts of alcohol, 6.3-6.8 parts sour, ester
Change 0.01 part of catalyst, 0.2-0.6 parts of bion succinic acid, 0.004-0.005 parts of curing accelerator.
The alcohol is one or more of neopentyl glycol, ethylene glycol, 2- methyl-1,3-propanediols, trimethylolpropane；
The neopentyl glycol, ethylene glycol, 2- methyl-1,3-propanediols, trimethylolpropane mass ratio be 3.6-4.05：0-0.2：0-
0.3：0-0.05；
The acid is several in terephthalic acid (TPA), M-phthalic acid, adipic acid；The terephthalic acid (TPA), isophthalic diformazan
Sour, adipic acid mass ratio is 5.5-5.8：0.4-0.75：0-0.2；
The esterification catalyst is Mono-n-butyltin；
The curing accelerator is Ethyltriphenylphosphonium brimide；
The polyester resin is prepared by the following method, the specific steps are：
A, the first stage：By 3.6-4.1 parts of alcohol, 5.5-5.8 parts of terephthalic acid (TPA), 0.01 part of esterification catalyst and water 1
Part input reaction kettle, heating reaction kettle simultaneously open stirring, are to slowly warm up to 245~248 DEG C, maintain reaction to acid value be 7~
11mgKOH/g；
The heating rate of the heating is 1-10 DEG C/min, specially：180 DEG C are first warming up to, then with 2-5 DEG C/30min
It is warming up to 190 DEG C, after being warming up to 210 DEG C, 210 DEG C after 190 with 1-5 DEG C/30min, 245 are warming up to 10 DEG C/30min~
248℃；
B, second stage：Kettle temperature is down to 210~230 DEG C, 0.4-0.75 parts of M-phthalic acid of input, adipic acid 0-0.2
0.2-0.6 parts of part and bion succinic acid then heat to 230~240 DEG C, and it is 44~48mgKOH/g to maintain reaction to acid value；
C, the phase III：Under the conditions of 230-240 DEG C, 2~3h is vacuumized with vacuum degree -0.09~-0.10MPa, makes acid
It is worth for 30~35mgKOH/g, kettle temperature is then down to 180~210 DEG C, puts into 0.004-0.005 part of curing accelerator, maintenance 15
~25min.
The terephthalic acid (TPA) of the first stage and second stage input, M-phthalic acid, adipic acid the sum of mass parts
It is 6.3-6.8 parts.
The present invention using bion succinic acid substitute part from petrochemical industry route and come non-renewable resources prepare polyester tree
Fat, it is environmentally protective, industry carbon emission is reduced, is a direction of PET industry sustainable development.The polyester resin is applied to
During powdery paints, plate face is clear, and levelling is excellent, and comprehensive performance is good.
Specific embodiment
The present invention is described in detail with reference to embodiment.
Embodiment 1
A kind of terminal carboxyl polyester resin, raw material components and its quality are shown in Table 1.
The preparation of polyester resin：
(1) first stage：Alcohol, terephthalic acid (TPA), Mono-n-butyltin and 1kg water are put into reaction kettle, heating reaction
Kettle simultaneously opens stirring, is first warming up to 180 DEG C, is then warming up to 190 DEG C with 2 DEG C/30min, is heated up after 190 with 1 DEG C/30min
To after 210 DEG C, 210 DEG C, with 248 DEG C of 10 DEG C/30min, it is 9.3mgKOH/g to maintain reaction to acid value；
(2) second stage：Kettle temperature is down to 228 DEG C, puts into M-phthalic acid, adipic acid and bion succinic acid, then
240 DEG C are warming up to, it is 46.3mgKOH/g to maintain reaction to acid value；
(3) phase III：Under the conditions of 235 DEG C, 2.5h is vacuumized with vacuum degree -0.096MPa, acid value is
Then kettle temperature is down to 190 DEG C by 33.1mgKOH/g, put into Ethyltriphenylphosphonium brimide, maintains 20min.
The raw material and quality of each stage input are shown in Table 1.
Embodiment 2
A kind of terminal carboxyl polyester resin, raw material components and its quality are shown in Table 1.
The preparation of polyester resin：
(1) first stage：Alcohol, terephthalic acid (TPA), Mono-n-butyltin and 1kg water are put into reaction kettle, heating reaction
Kettle simultaneously opens stirring, is first warming up to 180 DEG C, is then warming up to 190 DEG C with 4 DEG C/30min, after 190-heated up with 3 DEG C/30min
To after 210 DEG C, 210 DEG C, 247 DEG C are warming up to 10 DEG C/30min, it is 10.6mgKOH/g to maintain reaction to acid value；
(2) second stage：Kettle temperature is down to 220 DEG C, M-phthalic acid and bion succinic acid is put into, then heats to
238 DEG C, it is 45.8mgKOH/g to maintain reaction to acid value；
(3) phase III：Under the conditions of 230 DEG C, 2.8h is vacuumized with vacuum degree -0.098MPa, acid value is
Then kettle temperature is down to 200 DEG C by 32.8mgKOH/g, put into Ethyltriphenylphosphonium brimide, maintains 15min.
The raw material and quality of each stage input are shown in Table 1.
Embodiment 3
A kind of terminal carboxyl polyester resin, raw material components and its quality are shown in Table 1.
The preparation of polyester resin：
(1) first stage：Alcohol, terephthalic acid (TPA), Mono-n-butyltin and 1kg water are put into reaction kettle, heating reaction
Kettle simultaneously opens stirring, is first warming up to 180 DEG C, is then warming up to 190 DEG C with 3 DEG C/30min, is heated up after 190 with 2 DEG C/30min
To after 210 DEG C, 210 DEG C, 247 DEG C are warming up to 10 DEG C/30min, it is 10.1mgKOH/g to maintain reaction to acid value；
(2) second stage：Kettle temperature is down to 229 DEG C, puts into M-phthalic acid, adipic acid and bion succinic acid, then
235 DEG C are warming up to, it is 47.5mgKOH/g to maintain reaction to acid value；
(3) phase III：Under the conditions of 230 DEG C, 3h, acid value 34.0mgKOH/ are vacuumized with vacuum degree -0.090MPa
Then kettle temperature is down to 205 DEG C by g, put into Ethyltriphenylphosphonium brimide, maintains 22min.
The raw material and quality of each stage input are shown in Table 1.
Embodiment 4
A kind of terminal carboxyl polyester resin, raw material components and its quality are shown in Table 1.
The preparation of polyester resin：
(1) first stage：Alcohol, terephthalic acid (TPA), Mono-n-butyltin and 1kg water are put into reaction kettle, heating reaction
Kettle simultaneously opens stirring, is first warming up to 180 DEG C, is then warming up to 190 DEG C with 3 DEG C/30min, is heated up after 190 with 5 DEG C/30min
To after 210 DEG C, 210 DEG C, 245 DEG C are warming up to 10 DEG C/30min, it is 7.8mgKOH/g to maintain reaction to acid value；
(2) second stage：Kettle temperature is down to 230 DEG C, M-phthalic acid and bion succinic acid is put into, then heats to
240 DEG C, it is 44.9mgKOH/g to maintain reaction to acid value；
(3) phase III：Under the conditions of 235 DEG C, 2h, acid value 32.3mgKOH/ are vacuumized with vacuum degree -0.099MPa
Then kettle temperature is down to 200 DEG C by g, put into Ethyltriphenylphosphonium brimide, maintains 15min.
The raw material and quality of each stage input are shown in Table 1.
Embodiment 5
A kind of terminal carboxyl polyester resin, raw material components and its quality are shown in Table 1.
The preparation of polyester resin：
(1) first stage：The alcohol of formula ratio, terephthalic acid (TPA), Mono-n-butyltin and 1kg water are put into reaction kettle,
Heating reaction kettle simultaneously open stirring, be first warming up to 180 DEG C, be then warming up to 190 DEG C with 2 DEG C/30min, after 190-with 2 DEG C/
30min is warming up to after 210 DEG C, 210 DEG C, and 246 DEG C are warming up to 10 DEG C/30min, and it is 8.8mgKOH/ to maintain reaction to acid value
g；
(2) second stage：Kettle temperature is down to 225 DEG C, M-phthalic acid and bion succinic acid is put into, then heats to
237 DEG C, it is 46.8mgKOH/g to maintain reaction to acid value；
(3) phase III：Under the conditions of 235 DEG C, 2.6h is vacuumized with vacuum degree -0.095MPa, acid value is
Then kettle temperature is down to 203 DEG C by 33.5mgKOH/g, put into Ethyltriphenylphosphonium brimide, maintains 23min.
The raw material and quality of each stage input are shown in Table 1.
Examples 1 to 5 acid, alcohol, esterification catalyst, bion succinic acid, curing accelerator input amount be shown in Table 1.
1 each substance input amount (unit of table:kg)
The performance of polyester resin A~E prepared by Examples 1 to 5 is as shown in table 2
The performance indicator of 2 A of table~E
It will be applied on powdery paints respectively according to polyester resin made from Examples 1 to 5 method, the application process is
Polyester resin, curing agent, levelling agent, titanium dioxide, auxiliary agent, optical brightener, filler by formula rate are uniformly mixed, pass through twin-screw
Extruder squeezes out, tabletting, crushes, is sieved, electrostatic spraying after cooling.Each group distribution ratio is shown in Table 3.The curing agent is Hua Hui companies
TGIC, levelling agent is the PV88 of De Xinli Chemical Co., Ltd.s of Germany, and auxiliary agent is styrax, and optical brightener is chemical for the Ningbo South Sea
The 701B of Co., Ltd；The filler is the ultra-fine barium of Qingdao Dongfeng Auto Company.
3 each group distribution ratio (unit of table:g)
Coating obtained is tested for the property according to national standard, gel time is tested according to GB/T 16995-1997, gloss
It is tested according to GB/T9754-2007, impacts and tested according to GB/T 1732-1993, the results are shown in Table 4.
4 coating performance of table
From test result as can be seen that coating has to base material good adhesive force, impact and bending performance are good, simultaneously
Coating surface is clear, and levelling, chemical-resistance are more excellent.Polyester resin feed stock uses bion succinic acid, reduces entire
Industry carbon emission reduces the consumption of non-renewable resources, has a extensive future.
Claims (6)
1. a kind of terminal carboxyl polyester resin, raw material components and its mass parts are：3.6-4.1 parts of alcohol, 6.3-6.8 parts sour, esterification
0.01 part of catalyst, 0.2-0.6 parts of bion succinic acid, 0.004-0.005 parts of curing accelerator.
The alcohol is one or more of neopentyl glycol, ethylene glycol, 2- methyl-1,3-propanediols, trimethylolpropane；It is described
Neopentyl glycol, ethylene glycol, 2- methyl-1,3-propanediols, trimethylolpropane mass ratio be 3.6-4.05：0-0.2：0-0.3：
0-0.05；
The acid is several in terephthalic acid (TPA), M-phthalic acid, adipic acid；The terephthalic acid (TPA), M-phthalic acid, oneself
The mass ratio of diacid is 5.5-5.8：0.4-0.75：0-0.2.
2. polyester resin as described in claim 1, it is characterised in that：The esterification catalyst is Mono-n-butyltin.
3. polyester resin as described in claim 1, it is characterised in that：The curing accelerator is Ethyltriphenylphosphonium brimide.
4. a kind of terminal carboxyl polyester resin, step include：
A, the first stage：By 0.01 part of 3.6-4.1 parts of alcohol, 5.5-5.8 parts of terephthalic acid (TPA), esterification catalyst input reaction kettle,
Heating reaction kettle simultaneously opens stirring, is to slowly warm up to 245~248 DEG C, and it is 7~11mgKOH/g to maintain reaction to acid value；
B, second stage：Kettle temperature is down to 210~230 DEG C, 0.4-0.75 parts of M-phthalic acid of input, 0-0.2 parts of adipic acid and
0.2-0.6 parts of bion succinic acid then heats to 230~240 DEG C, and it is 44~48mgKOH/g to maintain reaction to acid value；
C, the phase III：Under the conditions of 230-240 DEG C, 2~3h is vacuumized with vacuum degree -0.09~-0.10MPa, makes the acid value be
Then kettle temperature is down to 180~210 DEG C by 30~35mgKOH/g, put into 0.004-0.005 part of curing accelerator, and maintenance 15~
25min。
The terephthalic acid (TPA) of the first stage and second stage input, M-phthalic acid, adipic acid the sum of mass parts be
6.3-6.8 part.
5. preparation method as claimed in claim 4, it is characterised in that：The heating rate to heat up in the step A for 1-10 DEG C/
min。
6. preparation method as claimed in claim 5, it is characterised in that：The heating rate of the heating is：First it is warming up to 180
DEG C, 190 DEG C, after being warming up to 210 DEG C, 210 DEG C after 190 with 1-5 DEG C/30min then are warming up to 2-5 DEG C/30min, with
10 DEG C/30min is warming up to 245~248 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711406643.6A CN108129643A (en) | 2017-12-22 | 2017-12-22 | A kind of terminal carboxyl polyester resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711406643.6A CN108129643A (en) | 2017-12-22 | 2017-12-22 | A kind of terminal carboxyl polyester resin and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734882A (en) * | 2018-11-30 | 2019-05-10 | 安徽神剑新材料股份有限公司 | A kind of three-glycidyl isocyanurate curing thermal transfer powdery paints carboxyl end group saturated polyester resin and its synthetic method |
| CN110563934A (en) * | 2019-09-09 | 2019-12-13 | 安徽神剑新材料股份有限公司 | Fingerprint-resistant polyester resin and preparation method thereof |
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Application publication date: 20180608 |