CN107459638A - A kind of PBST resins and preparation method thereof - Google Patents
A kind of PBST resins and preparation method thereof Download PDFInfo
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- CN107459638A CN107459638A CN201710531077.5A CN201710531077A CN107459638A CN 107459638 A CN107459638 A CN 107459638A CN 201710531077 A CN201710531077 A CN 201710531077A CN 107459638 A CN107459638 A CN 107459638A
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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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—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
-
- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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- 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)
- Polyesters Or Polycarbonates (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of PBST resins and preparation method thereof, including：（a）Mutual-phenenyl two acid bromide two alcohol ester's unit；（b）Decanedioic acid butanediol ester unit；（c）Isocyanates；Wherein, the gross weight based on PBST resins, the weight content of isocyanates are 0.31% 0.59%.The present invention is in PBST resins, by adding a small amount of isocyanates, and by the control of the content of isocyanates in the range of 0.31% 0.59%, the content of end carboxyl in polyester molecule chain can not only be reduced, and the reflecting point of side chain can be drawn in the strand of generation, polymer molecule is set to produce a certain degree of crosslinking, form network structure, so that the PBST resins being prepared are after 95 DEG C of boilings 12 hours, melting means amplitude of variation is less than 15, relative viscosity amplitude of variation is less than 0.22, has the water boiling resistance ageing properties being obviously improved.
Description
Technical field
The invention belongs to synthesis of polymer material field, and in particular to a kind of PBST trees with good water boiling resistance aging
Fat and preparation method thereof.
Background technology
Degraded polyester material has been widely used, such as film, expanded material, Injection moulded part.Such material has good
Good physical property, and water and carbon dioxide can be degraded under compost or nature, there is no potential danger to environment
Evil.Wherein, poly- decanedioic acid butylene terephthalate resin（PBST）It is very active in current biodegradable plastic research
One of degradable material.However, such materials most is made up of aliphatic polyester or aliphatic/aromatic copolyester, in height
Anti-hydrolytic performance is bad under warm moist environment, or during processing, due to the presence of a small amount of moisture, and causes material
Degraded.The hydrolytic degradation of polyester resin is due to the ester bond in water molecules attack polyester molecule and causes macromolecule chain break,
And the end carboxyl and can on polyester molecule chain accelerates the hydrolytic cleavage of ester bond.Therefore, by controlling the end carboxyl of polyester resin
Content, the hydrolytic stability of polyester material can be improved.
The present invention through research surprisingly it has been found that, add a small amount of isocyanates in PBST resins, and by isocyanates
Content controls within the specific limits, and the PBST resins that can make to be prepared have good water boiling resistance ageing properties.
The content of the invention
It is an object of the invention to provide a kind of PBST resins, the PBST resins have the water boiling resistance aging being obviously improved
Energy.
The present invention is achieved by the following technical solutions：
A kind of PBST resins, including：
（a）Mutual-phenenyl two acid bromide two alcohol ester's unit；
（b）Decanedioic acid butanediol ester unit；
（c）Isocyanates；
Wherein, the gross weight based on PBST resins, the weight content of isocyanates is 0.31%-0.59%.
The weight content assay method of the isocyanates：It is measured using elemental analyser, by 0.1-0.5gPBST
Make its combustion decomposition through catalysis oxidation in oxygen atmosphere of the resin sample under 1150 DEG C of high temperature, generate the non-detection gas in gas
Body is removed, and detected nitrogen reuses thermal conductivity detector (TCD) and nitrogen is detected, determine nitrogen member by adsorption column separation
The content of element, and the content of isocyanates is converted into according to the content of nitrogen, wherein helium is as carrier gas and purge gass, furnace temperature
It is set as 1150 DEG C, each sample test takes arithmetic mean of instantaneous value three times.
PBST resins of the present invention are decanedioic acid butanediol ester and the copolymer of mutual-phenenyl two acid bromide two alcohol ester, in height
Anti-hydrolytic performance is bad under warm moist environment, or during processing, due to the presence of a small amount of moisture, and causes material
Degraded, cause the disconnected of macromolecular chain the reason for its hydrolytic degradation mainly due to the ester bond in water molecules attack polyester molecule
Split, and the end carboxyl and can on polyester molecule chain accelerates the hydrolytic cleavage of ester bond.And the present invention is had found by studying, in PBST
By adding a small amount of isocyanates in resin synthesis process, and the content of isocyanates is controlled in 0.31%-0.59% scopes
It is interior, the content of end carboxyl in polyester molecule chain can be reduced, and the reflecting point of side chain can be drawn in the strand of generation, make
Polymer molecule produces a certain degree of crosslinking, forms network structure, substantially changes so that the PBST resins being prepared have
Kind water boiling resistance ageing properties.
If the content of isocyanates is too low in PBST resins, the work for reducing the content of carboxyl end group on polyester molecule chain is not had
With, if the too high levels of isocyanates, crosslinked polymer can be made excessive, after 95 DEG C of boilings 12 hours, melting means change is more than 15,
Relative viscosity change is more than 0.22, and water boiling resistance ageing properties reduce, therefore, based on the gross weight of PBST resins, isocyanates
Weight content is preferably 0.35%-0.45%.
Wherein, the weight content T% of mutual-phenenyl two acid bromide two alcohol ester's unit is 30wt%-60wt% in the PBST resins.
When T% is less than 30wt%, the product made is too soft, is unfavorable for using, and when T% is higher than 60wt%, product is too hard, is unfavorable for using.
Wherein, for the PBST resins after 95 DEG C of boilings 12 hours, melt index amplitude of variation is less than 15, wherein, melting
Index is according to GB/T 3682-2000 standard tests, and temperature is 190 DEG C, load 2.16Kg.
Wherein, for the PBST resins after 95 DEG C of boilings 12 hours, relative viscosity amplitude of variation is less than 0.22, wherein, phase
Assay method to viscosity is：With phenol -- o-dichlorohenzene mixed liquor（Mass ratio 3:2）For solvent, determined using Ubbelohde viscometer
Relative viscosity during 25 DEG C of sample, sample concentration 0.005g/mL,
Relative viscosity calculates formula：ηr=t/t0；
η in formular--- relative viscosity；
The delivery time of t--- sample solutions, s；
t0--- the delivery time of neat solvent, s.
The present invention also provides the preparation method of above-mentioned PBST resins, comprises the following steps：
By in the terephthalic acid (TPA) of metering and BDO input reactor, with being warming up to 240 DEG C -260 DEG C after nitrogen displacement,
After reacting 2-4 hours, decanedioic acid is added, 240 DEG C -260 DEG C is warming up to and continues to react 2-4 hours, addition accounts for PBST resin gross weights
0.1-0.7wt% titanate ester catalyst is measured, reacting kettle inner pressure is then reduced to below 50Pa in 30min, 240
DEG C -260 DEG C continue to react 2-5 hours, stop stirring, are eventually adding isocyanates reaction 5-30 minutes, are filled with into reactor
High pure nitrogen, resin is extruded from reactor, is granulated, obtains PBST resins.
The titanate ester catalyst can be four (2- ethylhexyls) titanate esters.
The present invention compared with prior art, has the advantages that：
The present invention is controlled in 0.31%- in PBST resins by adding a small amount of isocyanates, and by the content of isocyanates
In the range of 0.59%, the content of end carboxyl in polyester molecule chain can be not only reduced, and branch can be drawn in the strand of generation
The reflecting point of chain, polymer molecule is produced a certain degree of crosslinking, network structure is formed, so that the PBST trees being prepared
For fat after 95 DEG C of boilings 12 hours, melting means amplitude of variation is less than 15, and relative viscosity amplitude of variation is less than 0.22, has and is obviously improved
Water boiling resistance ageing properties.
Embodiment
The present invention is further illustrated below by embodiment, following examples are the preferable embodiment party of the present invention
Formula, but embodiments of the present invention are not limited by following embodiments.
Raw material derives from purchased in market needed for the present invention.
Resin syntheses processes：
As shown in table 1, by the terephthalic acid (TPA) of metering and BDO input reactor, with being warming up to after nitrogen displacement
240 DEG C -260 DEG C, after reacting 2-4 hours, decanedioic acid is added, 240 DEG C -260 DEG C is warming up to and continues to react 2-4 hours, addition accounts for
PBST total resin weights 0.1-0.7wt% four (2- ethylhexyls) titanate esters, then drop reacting kettle inner pressure in 30min
As little as below 50Pa, continue to react 2-5 hours at 240 DEG C -260 DEG C, stop stirring, be eventually adding 5-30 points of isocyanates reaction
Clock, high pure nitrogen is filled with into reactor, resin is extruded from reactor, is granulated, obtains PBST resins.Change terephthaldehyde
The inventory of acid and decanedioic acid, you can obtain the PBST resins of different mutual-phenenyl two acid bromide two alcohol ester's unit contents.
Wherein mutual-phenenyl two acid bromide two alcohol ester's unit content passes through1H NMR are tested, and using deuterochloroform as solvent, TMS is interior
Mark, is as a result calculated according to the following formula：
Wherein：T% is mutual-phenenyl two acid bromide two alcohol ester's unit content；
S8.1For1Peak area is absorbed in H NMR spectras at 8.1ppm；
S2.3For1Peak area is absorbed in H NMR spectras at 2.3ppm；
Change the addition of isocyanates, you can obtain the PBST resins of different isocyanate contents.The PBST that will be prepared
It is as shown in table 2 to test its results of property after 95 DEG C of boilings 12 hours for resin.
Table 1
Performance test standard：
Melt index determination：GB/T 3682-2000 standards, temperature are 190 DEG C, load 2.16Kg；
Relative viscosity determines：With phenol -- o-dichlorohenzene mixed liquor（Mass ratio 3:2）For solvent, sample is determined using Ubbelohde viscometer
Relative viscosity during 25 DEG C of product, sample concentration 0.005g/mL.
Relative viscosity calculates formula：ηr=t/t0 ;
η in formular--- relative viscosity；
The delivery time of t--- sample solutions, s；
t0--- the delivery time of neat solvent, s.
Isocyanate weight content assaying method：It is measured using elemental analyser, by 0.1-0.5gPBST resin-likes
Make its combustion decomposition through catalysis oxidation in oxygen atmosphere of the product under 1150 DEG C of high temperature, the non-detection gas generated in gas is gone
Remove, detected nitrogen reuses thermal conductivity detector (TCD) and nitrogen is detected, determine containing for nitrogen by adsorption column separation
Measure, and the content of isocyanates is converted into according to the content of nitrogen, wherein helium is set as carrier gas and purge gass, furnace temperature
1150 DEG C, each sample test takes arithmetic mean of instantaneous value three times.
The embodiment 1-8 of table 2 and comparative example 1-4 each components with when the performance test results
Note：Melt index-original the melt index of melt index amplitude of variation=after 95 DEG C of boilings 12 hours；
The relative viscosity of relative viscosity amplitude of variation=original relative viscosity-after 95 DEG C of boilings 12 hours；
From Table 2, it can be seen that when the content of isocyanates is 0.31-0.59% in PBST resins, through 95 DEG C of boilings 12 hours
Afterwards, melt index amplitude of variation is less than 15, and relative viscosity amplitude of variation is less than 0.22, shows that there is resin well water-fast to over-cooked
Change performance, can solve the stability of polymer performance in storage and process, and the performance of such polyester articles can be improved
Conservation rate.And when the content of isocyanates is less than 0.31% or higher than 0.59% in comparative example 1-4, melt index amplitude of variation is big
In 15, relative viscosity amplitude of variation is more than 0.22, shows that PBST resin water boiling resistance ageing properties are poor.
Claims (7)
- A kind of 1. PBST resins, it is characterised in that including：（a）Mutual-phenenyl two acid bromide two alcohol ester's unit；（b）Decanedioic acid butanediol ester unit；（c）Isocyanates；Wherein, the gross weight based on PBST resins, the weight content of isocyanates is 0.31%-0.59%.
- A kind of 2. PBST resins according to claim 1, it is characterised in that the weight content measure side of the isocyanates Method：It is measured, will be passed through in oxygen atmosphere of the 0.1-0.5gPBST resin samples under 1150 DEG C of high temperature using elemental analyser Catalysis oxidation makes its combustion decomposition, and the non-detection gas generated in gas is removed, detected nitrogen by adsorption column separation, Reuse thermal conductivity detector (TCD) to detect nitrogen, determine the content of nitrogen, and be converted into according to the content of nitrogen different The content of cyanate, wherein helium are as carrier gas and purge gass, and furnace temperature is set as 1150 DEG C, and each sample test takes arithmetic three times Average value.
- 3. a kind of PBST resins according to claim 1, it is characterised in that the gross weight based on PBST resins, isocyanic acid The weight content of ester is 0.35%-0.45%.
- A kind of 4. PBST resins according to claim 1, it is characterised in that the gross weight based on PBST resins is described right The weight content T% of benzene dicarboxylic acid butanediol ester unit is 30wt%-60wt%.
- 5. a kind of PBST resins according to claim any one of 1-4, it is characterised in that the PBST resins are through 95 DEG C of water After boiling 12 hours, melt index amplitude of variation is less than 15, wherein, melt index is according to GB/T 3682-2000 standard tests, temperature Spend for 190 DEG C, load 2.16Kg.
- 6. a kind of PBST resins according to claim any one of 1-4, it is characterised in that the PBST resins are through 95 DEG C of water After boiling 12 hours, relative viscosity amplitude of variation is less than 0.22, wherein, the assay method of relative viscosity is：With phenol -- adjacent dichloro Benzene mixed liquor（Mass ratio 3:2）For solvent, using relative viscosity during 25 DEG C of Ubbelohde viscometer determination sample, sample concentration is 0.005g/mL,Relative viscosity calculates formula：ηr=t/t0；η in formular--- relative viscosity；The delivery time of t--- sample solutions, s；t0--- the delivery time of neat solvent, s.
- 7. the preparation method of a kind of PBST resins according to claim any one of 1-6, it is characterised in that including following step Suddenly：By in the terephthalic acid (TPA) of metering and BDO input reactor, with being warming up to 240 DEG C -260 DEG C after nitrogen displacement, After reacting 2-4 hours, decanedioic acid is added, 240 DEG C -260 DEG C is warming up to and continues to react 2-4 hours, addition accounts for PBST resin gross weights 0.1-0.7wt% titanate ester catalyst is measured, reacting kettle inner pressure is then reduced to below 50Pa in 30min, 240 DEG C -260 DEG C continue to react 2-5 hours, stop stirring, are eventually adding isocyanates reaction 5-30 minutes, are filled with into reactor High pure nitrogen, resin is extruded from reactor, is granulated, obtains PBST resins.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102007159A (en) * | 2008-04-15 | 2011-04-06 | 巴斯夫欧洲公司 | Method for the continuous production of biodegradable polyesters |
| CN102164984A (en) * | 2008-09-29 | 2011-08-24 | 巴斯夫欧洲公司 | Aliphatic-aromatic polyester |
| CN102712766A (en) * | 2009-11-09 | 2012-10-03 | 巴斯夫欧洲公司 | Method for producing shrink films |
| CN104927036A (en) * | 2015-06-09 | 2015-09-23 | 广东天龙油墨集团股份有限公司 | Preparation methods for polyester polyol and alcohol-soluble plastic printing ink polyurethane bonding material |
-
2017
- 2017-07-03 CN CN201710531077.5A patent/CN107459638A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102007159A (en) * | 2008-04-15 | 2011-04-06 | 巴斯夫欧洲公司 | Method for the continuous production of biodegradable polyesters |
| CN102164984A (en) * | 2008-09-29 | 2011-08-24 | 巴斯夫欧洲公司 | Aliphatic-aromatic polyester |
| CN102712766A (en) * | 2009-11-09 | 2012-10-03 | 巴斯夫欧洲公司 | Method for producing shrink films |
| CN104927036A (en) * | 2015-06-09 | 2015-09-23 | 广东天龙油墨集团股份有限公司 | Preparation methods for polyester polyol and alcohol-soluble plastic printing ink polyurethane bonding material |
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