CN109232868A - A kind of polyester resin of engineering plastics and the preparation method and application thereof - Google Patents
A kind of polyester resin of engineering plastics and the preparation method and application thereof Download PDFInfo
- Publication number
- CN109232868A CN109232868A CN201810984702.6A CN201810984702A CN109232868A CN 109232868 A CN109232868 A CN 109232868A CN 201810984702 A CN201810984702 A CN 201810984702A CN 109232868 A CN109232868 A CN 109232868A
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- Prior art keywords
- acid
- polyester resin
- engineering plastics
- preparation
- polyester
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Classifications
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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
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- 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
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
-
- 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
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
Abstract
The present invention provides a kind of polyester resin of engineering plastics, it is characterised in that: the inherent viscosity of the polyester resin is 0.5~1.0dl/g, and glass transition temperature is greater than 120 DEG C；Its ingredient is by comprising the dihydric alcohol structural unit and dicarboxylic acid structural units' composition including the bis- camphor-PEARLITOL 25Cs of 2,4:3,5-, the molar ratio that the bis- camphor-PEARLITOL 25Cs of 2,4:3,5- account for total dihydric alcohol structural unit is 30~60%.The beneficial effects of the present invention are embodied in: the special spirane structure of monomer, it is set to have very high rigidity and toughness, glass transition temperature is greater than 120 DEG C, so that the polyester has better machinability, good color, heat resistance, dimensional stability and mechanical property.
Description
Technical field
The present invention relates to the polyester resin and the preparation method and application thereof that a kind of rigidity of engineering plastics is strong and toughness is high.
Background technique
PET (polyethylene terephthalate) is industrial valuable polyester because its very good mechanical properties and
Lower cost.For example, PET has been widely used in various applications, such as fiber, tyre cord, in bottle and film.But it is needing
PET nevertheless suffers from very big limitation when the use of more high stability and heat resistance aspect of performance.Therefore it is badly in need of developing one kind
It must can remain dimensionally-stable under heating and the polyester resin of more high strength.
Summary of the invention
In order to solve the deficiencies in the prior art, the present invention provides a kind of polyester resin of engineering plastics and its preparation sides
Method and application.
The purpose of the present invention is achieved through the following technical solutions:
A kind of polyester resin of engineering plastics, the inherent viscosity of the polyester resin are 0.5~1.0dl/g, glass transition
Temperature is greater than 120 DEG C；Its ingredient is by including the dihydric alcohol structural unit and dicarboxylic acids including the bis- camphor-PEARLITOL 25Cs of 2,4:3,5-
Structural unit composition, the bis- camphor-PEARLITOL 25Cs of 2,4:3,5- account for the molar ratio of total dihydric alcohol structural unit for 30~
60%。
Wherein, the inherent viscosity of the polyester resin is using phenol and 1, and the mass ratio of 1,2,2- tetrachloroethanes is 6:4
Measured value of the mixed solvent at 25 DEG C.
Preferably, the dicarboxylic acid structural units are from terephthalic acid (TPA), M-phthalic acid, phthalic acid, 2- first
Base terephthalic acid (TPA), diphenyl dicarboxylic acid, tetrahydronaphthalene dicarboxylic acids, naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
Suberic acid, azelaic acid, decanedioic acid, decane dicarboxylic acid, dodecanedicarboxylic acid, cyclohexane dicarboxylic acid, in decahydronaphthalenes dicarboxylic acids
One or more kinds of any combination.
Preferably, the dihydric alcohol structural unit is from including aliphatic diol compound or aromatic diol compound
At least one of compound.
Preferably, the preparation method of the polyester resin of a kind of engineering plastics, using ontology melt copolymerization method into
Row preparation, includes the following steps,
S1, dicarboxylic acids, dihydric alcohol, the bis- camphor-PEARLITOL 25Cs of 2,4:3,5- are put into reaction kettle, under nitrogen protection, is stirred
It mixes uniformly, is reacted 0.2~0.3 hour at 60~100 DEG C；
S2, it is gradually warmed up at 220 DEG C, insulation reaction 1~1.5 hour, then is warming up to 230~270 DEG C and reacts 2~2.5 hours,
When amount of by-products reaches theoretical value out, reaction was completed；
S3, polyester polycondensation catalyst and stabilizer is added, continues to heat up and slowly depressurize, carry out revolving speed and adjust to 30~50rpm,
Temperature controls between 275~295 DEG C, and decompression step by step to 100Pa or less carries out polycondensation reaction；
S4, sampling analysis stop stirring when polymer viscosity reaches desired value, eliminate vacuum, and product discharge is obtained for work
The polyester resin of engineering plastics.
Preferably, the mixing speed in the S1 is greater than mixing speed in the S3.
Preferably, it is reacted 2.2 hours when being warming up to 230~270 DEG C in the S2.
Preferably, in the S3 polyester polycondensation catalyst include and be not limited to antimony acetate, antimony acetate, butyl titanate,
Isopropyl titanate, sodium acetate, zinc acetate, manganese acetate, dibutyltin oxide, antimony glycol, antimony oxide.
Preferably, stabilizer includes and is not limited to phosphoric acid and its carboxylate or phosphorous acid and its carboxylate in the S3.
Preferably, the application of the polyester resin of above-described a kind of engineering plastics, the polyester resin is for making
Standby sheet material, film or fiber, including all kinds of Bottle & Cans, pallet, stick tubing product.
The beneficial effects of the present invention are embodied in: bis- camphor-PEARLITOL 25Cs of 2,4:3,5- contain 8 cyclic structures including
Spirane structure, multiple cyclic structures keep the steric hindrance of monomer especially big, and glass transition temperature is high, while can protect ester
Key, so that final products stability is good.Polyester resin of the invention has very high rigidity and toughness, glass transition temperature
Greater than 120 DEG C, there is better machinability, good color, heat resistance, dimensional stability and mechanical property.
Specific embodiment
It is specifically described technical solution of the present invention with reference to embodiments, present invention discloses a kind of the rigid of engineering plastics
The strong and high toughness polyester resin and the preparation method and application thereof of property.
Embodiment 1
By terephthalic acid (TPA) 13.3kg, M-phthalic acid 3.3kg, the bis- camphor-PEARLITOL 25Cs of ethylene glycol 4.4kg, 2,4:3,5-
23.8kg is put into 100L stainless steel cauldron, under nitrogen protection, with the stirring of 55~80rpm revolving speed, be rapidly heated to
It after 60~100 DEG C are reacted 0.3 hour, is gradually warmed up to 220 DEG C of heat preservations and carries out reaction 1 hour, then be warming up to 230~270 DEG C instead
It answers 2.2 hours or so, when amount of by-products reaches theoretical value out, reaction was completed.Addition zinc acetate 28g, isopropyl titanate 28g,
The antimony acetate of 24g and the triphenyl phosphate of 15g continue to heat up and slowly depressurize, and revolving speed is adjusted to 30~50rpm, temperature control
To between 275~295 DEG C, decompression step by step to 100Pa or less carries out polycondensation reaction.Sampling analysis, when polymer viscosity reaches pre-
Stop stirring when time value, eliminate vacuum, product discharge obtains the polyester resin for engineering plastics.
Embodiment 2
By terephthalic acid (TPA) 8.3kg, naphthalenedicarboxylic acid 10.7kg, the bis- camphor-D- of 1,4 cyclohexane dimethanol 11.5kg, 2,4:3,5-
Mannitol 15.9kg is put into 100L stainless steel cauldron, under nitrogen protection, is stirred with 55~80rpm revolving speed, quickly
After being warming up to 60~100 DEG C of reactions 0.3 hour, it is gradually warmed up to 220 DEG C of heat preservations and carries out reaction 1 hour, then it is warming up to 230~
270 DEG C are reacted 2.2 hours or so, and when amount of by-products reaches theoretical value out, reaction was completed.The antimony acetate and 15g of 24g is added
Triphenyl phosphate continues to heat up and slowly depressurize, and revolving speed is adjusted to 30~50rpm, and temperature is controlled between 275~295 DEG C, by
Step is depressurized to 100Pa or less and carries out polycondensation reaction.Sampling analysis stops stirring when polymer viscosity reaches desired value, eliminates
Vacuum, product discharge obtain the polyester resin for engineering plastics.
Embodiment 3
By terephthalic acid (TPA) 16.6kg, ethylene glycol 1.2kg, the bis- camphor-D- sweet dews of 1,4 cyclohexane dimethanol 5kg, 2,4:3,5-
Alcohol 17.9kg is put into 100L stainless steel cauldron, under nitrogen protection, with the stirring of 55~80rpm revolving speed, is rapidly heated
After being reacted 0.3 hour to 60~100 DEG C, it is gradually warmed up to 220 DEG C of heat preservations and carries out reaction 1 hour, then be warming up to 230~270 DEG C
Reaction 2.2 hours or so, when amount of by-products reaches theoretical value out, reaction was completed.The antimony oxide of 21g and the phosphorus of 16g is added
Triphenyl phosphate ester continues to heat up and slowly depressurize, and revolving speed is adjusted to 30~50rpm, and temperature is controlled between 275~295 DEG C, gradually
It is depressurized to 100Pa or less and carries out polycondensation reaction.Sampling analysis stops stirring when polymer viscosity reaches desired value, eliminates true
Sky, product discharge obtain the polyester resin for engineering plastics.
Embodiment 4
By terephthalic acid (TPA) 13.3kg, decanedioic acid 4kg, neopentyl glycol 5.2kg, 2,4:3,5- bis- camphors-PEARLITOL 25C 19.9kg
It puts into 100L stainless steel cauldron, under nitrogen protection, with the stirring of 55~80rpm revolving speed, is rapidly heated to 60~100
It DEG C after reaction 0.3 hour, is gradually warmed up to 220 DEG C of heat preservations and carries out reaction 1 hour, then to be warming up to 230~270 DEG C of reactions 2.2 small
When or so, when amount of by-products reaches theoretical value out, reaction was completed.The antimony glycol of 21g and the triphenyl phosphate of 16g is added, after
Temperature of continuing rising simultaneously slowly depressurizes, and revolving speed is adjusted to 30~50rpm, and temperature is controlled between 275~295 DEG C, decompression step by step to 100Pa
Polycondensation reaction is carried out below.Sampling analysis stops stirring when polymer viscosity reaches desired value, eliminates vacuum, product discharge
Obtain the polyester resin for engineering plastics.
Comparative example:
Commercially available PET material
Performance comparison:
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example |
| Inherent viscosity (dl/g) | 0.73 | 0.67 | 0.81 | 0.78 | 0.67 |
| Glass transition temperature (DEG C) | 137 | 153 | 142 | 129 | 70 |
| Breaking strength (N/mm) | 41 | 58 | 47 | 35 | 24 |
| Shore hardness (A) | 128 | 153 | 134 | 121 | 92 |
Passage capacity compares it can be found that polyester fiberglass transition temperature provided by the invention and breaking strength and hardness are all remote
It is higher by much more than commercially available PET material, is suitable as engineering plastics material, performance greatly improves.
Certainly still there are many specific embodiments by the present invention, are just not listed one by one herein.It is all using equivalent replacement or
Equivalent transformation and all technical solutions formed, all fall within the scope of protection of present invention.
Claims (9)
1. a kind of polyester resin of engineering plastics, it is characterised in that: the inherent viscosity of the polyester resin is 0.5~1.0dl/
G, glass transition temperature are greater than 120 DEG C；Its ingredient is by including the dihydric alcohol structure including the bis- camphor-PEARLITOL 25Cs of 2,4:3,5-
Unit and dicarboxylic acid structural units' composition, the bis- camphor-PEARLITOL 25Cs of 2,4:3,5- account for rubbing for total dihydric alcohol structural unit
Your ratio is 30~60%.
2. a kind of polyester resin of engineering plastics as described in claim 1, it is characterised in that: the dicarboxylic acid structural units
From: terephthalic acid (TPA), M-phthalic acid, phthalic acid, 2- methylterephthalic acid, diphenyl dicarboxylic acid, tetrahydronaphthalene
Dicarboxylic acids, naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, decane dicarboxylic acid,
One of dodecanedicarboxylic acid, cyclohexane dicarboxylic acid, decahydronaphthalenes dicarboxylic acids or more than one any combination.
3. a kind of polyester resin of engineering plastics as described in claim 1, it is characterised in that: the dihydric alcohol structural unit
From including at least one of aliphatic diol compound or aromatic diol compound compound.
4. a kind of preparation method of the polyester resin of engineering plastics as described in claim 1, it is characterised in that: use ontology
Prepared by melting copolymerization method, include the following steps,
S1, dicarboxylic acids, dihydric alcohol, the bis- camphor-PEARLITOL 25Cs of 2,4:3,5- are put into reaction kettle, under nitrogen protection, is stirred
It mixes uniformly, is reacted 0.2~0.3 hour at 60~100 DEG C；
S2, it is gradually warmed up to 220 DEG C, insulation reaction 1~1.5 hour, then is warming up to 230~270 DEG C and reacts 2~2.5 hours, when
Reaction was completed when amount of by-products reaches theoretical value out；
S3, polyester polycondensation catalyst and stabilizer is added, continues to heat up and slowly depressurize, carry out revolving speed and adjust to 30~50rpm,
Temperature controls between 275~295 DEG C, and decompression step by step to 100Pa or less carries out polycondensation reaction；
S4, sampling analysis stop stirring when polymer viscosity reaches desired value, eliminate vacuum, and product discharge is obtained for work
The polyester resin of engineering plastics.
5. a kind of preparation method of the polyester resin of engineering plastics as claimed in claim 5, it is characterised in that: in the S1
Mixing speed be greater than the S3 in mixing speed.
6. a kind of preparation method of the polyester resin of engineering plastics as claimed in claim 5, it is characterised in that: in the S2
It is reacted 2.2 hours when being warming up to 230~270 DEG C.
7. a kind of preparation method of the polyester resin of engineering plastics as claimed in claim 5, it is characterised in that: in the S3
Polyester polycondensation catalyst includes and is not limited to antimony acetate, butyl titanate, isopropyl titanate, sodium acetate, zinc acetate, acetic acid
Manganese, dibutyltin oxide, antimony glycol, antimony oxide.
8. a kind of preparation method of the polyester resin of engineering plastics as claimed in claim 5, it is characterised in that: in the S3
Stabilizer includes and is not limited to phosphoric acid and its carboxylate or phosphorous acid and its carboxylate.
9. a kind of application of the polyester resin of engineering plastics as described in claim 1, it is characterised in that: the polyester tree
Rouge is used to prepare including and is not limited to sheet material, film or fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810984702.6A CN109232868A (en) | 2018-08-28 | 2018-08-28 | A kind of polyester resin of engineering plastics and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810984702.6A CN109232868A (en) | 2018-08-28 | 2018-08-28 | A kind of polyester resin of engineering plastics and the preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109232868A true CN109232868A (en) | 2019-01-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810984702.6A Pending CN109232868A (en) | 2018-08-28 | 2018-08-28 | A kind of polyester resin of engineering plastics and the preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117354A (en) * | 2019-05-09 | 2019-08-13 | 苏州长业材料技术有限公司 | A kind of polyester resin for glass baseplate coating and preparation method thereof and coating |
| CN115044021A (en) * | 2022-06-23 | 2022-09-13 | 中瀚新材料科技有限公司 | Malonic acid branched polyester and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160103692A (en) * | 2015-02-25 | 2016-09-02 | 한양대학교 산학협력단 | Diol compounds derived from hexaol compounds, ester derivatives thereof and polymers thereof |
-
2018
- 2018-08-28 CN CN201810984702.6A patent/CN109232868A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160103692A (en) * | 2015-02-25 | 2016-09-02 | 한양대학교 산학협력단 | Diol compounds derived from hexaol compounds, ester derivatives thereof and polymers thereof |
Non-Patent Citations (1)
| Title |
|---|
| PARK, JEONG EON: "Thermally stable bio-based aliphatic polycarbonates with quadra-cyclic diol from renewable sources", 《MACROMOLECULAR RESEARCH》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117354A (en) * | 2019-05-09 | 2019-08-13 | 苏州长业材料技术有限公司 | A kind of polyester resin for glass baseplate coating and preparation method thereof and coating |
| CN110117354B (en) * | 2019-05-09 | 2021-05-25 | 中瀚新材料科技有限公司 | Polyester resin for glass substrate coating, preparation method thereof and coating |
| CN115044021A (en) * | 2022-06-23 | 2022-09-13 | 中瀚新材料科技有限公司 | Malonic acid branched polyester and preparation method thereof |
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Application publication date: 20190118 |