CN107474230A - A kind of PBAT resins and preparation method thereof - Google Patents
A kind of PBAT resins and preparation method thereof Download PDFInfo
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- CN107474230A CN107474230A CN201710531078.XA CN201710531078A CN107474230A CN 107474230 A CN107474230 A CN 107474230A CN 201710531078 A CN201710531078 A CN 201710531078A CN 107474230 A CN107474230 A CN 107474230A
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- pbat
- pbat resins
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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
- C08G63/68—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 Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
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Abstract
The invention discloses a kind of PBAT resins and preparation method thereof, including：（a）Mutual-phenenyl two acid bromide two alcohol ester's unit；（b）Tetramethylene adipate unit；（c）Isocyanates；Wherein, the gross weight based on PBAT resins, the weight content of isocyanates are 0.61% 0.75%.The present invention is in PBAT resins, can meet the rheological property of PBAT resins in the range of 0.61% 0.75% by adding a small amount of isocyanates, and by the content control of isocyanates：In shear rate 5000s 1, shear viscosity is less than or equal to 180 Pa*s more than 10 Pa*s, ensure to be crosslinked while the viscosity for improving PBAT resins ensures blown film stability excessively, and resin has the blown film characteristic being obviously improved, in fair speed blown film, membrane material obtains good film-forming property, and is not in the situation of holes and fisheye, ensure that the continuity of blown film production.
Description
Technical field
The invention belongs to synthesis of polymer material field, and in particular to a kind of PBAT with the blown film characteristic being obviously improved
Resin 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, polyadipate butylene terephthalate resin（PBAT）It is very active in current biodegradable plastic research
One of degradable material.However, polyadipate butylene terephthalate resin PBAT is in fair speed blown film, if resin sticks
Degree is too small, then the range of work is narrow, and processing conditions is difficult to control, and film bubble is unstable, and the film forming of resin is poor, it is not easy to is processed into
Film, if the viscosity of resin is too big, is easily caused in blow-molding process and plastify bad, the broken empty and fisheye of appearance, influence the property of film
Can be with blown film continuous production.
The present invention through research surprisingly it has been found that, by the way that the weight content of the isocyanates of PBAT resins is controlled in 0.61%-
In the range of 0.75%, it can make resin that there is the blown film characteristic being obviously improved, in fair speed blown film, membrane material obtains good film-forming property,
And be not in the situation of holes and fisheye, ensure that the continuity of blown film production.
The content of the invention
It is an object of the invention to provide a kind of PBAT resins, the PBAT resins have the blown film characteristic being obviously improved,
During fair speed blown film, membrane material obtains good film-forming property, and is not in the situation of holes and fisheye, ensure that the company of blown film production
Continuous property.
The present invention is achieved by the following technical solutions：
A kind of PBAT resins, including：
（a）Mutual-phenenyl two acid bromide two alcohol ester's unit；
（b）Tetramethylene adipate unit；
（c）Isocyanates；
Wherein, the gross weight based on PBAT resins, the weight content of isocyanates is 0.61%-0.75%.
The weight content assay method of the isocyanates：It is measured using elemental analyser, by 0.1-0.5gPBAT
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.
PBAT resins of the present invention are tetramethylene adipate and the copolymer of mutual-phenenyl two acid bromide two alcohol ester, this hair
It is bright to be found by studying, by adding a small amount of isocyanates in PBAT resins, and the content control of isocyanates is existed
In the range of 0.61%-0.75%, the viscosity that can improve PBAT resins ensures to be crosslinked while blown film stability is ensured
Degree, and resin has the blown film characteristic being obviously improved, in fair speed blown film, membrane material obtains good film-forming property, and is not in
The situation of holes and fisheye, it ensure that the continuity of blown film production.
If the content of isocyanates is too low in PBAT resins, melt strength is caused to decline, film bubble is unstable during blown film influences to blow
Membrane stability；Not had if the content of isocyanates is too low simultaneously reduces the effect of the content of carboxyl end group on polyester molecule chain,
So as to cause film degradation too fast, service life shortens；If the too high levels of isocyanates, crosslinked polymer can be made excessive, sticked
Degree is too big, and the appearance that plasticizing is bad, broken sky and fisheye occurs is easily caused in blow-molding process, influences performance and the blown film life of film
Continuity is produced, therefore, the present invention is had found by studying, is ensured while the viscosity for improving PBAT resins ensures blown film stability
It will not be crosslinked excessively, the shear viscosity of PBAT resins needs to be maintained to be less than or equal to 180Pa*s, preferably 50- more than 10Pa*s
150 Pa*s；Therefore, the gross weight based on PBAT resins, the weight content of isocyanates is preferably 0.65%-0.71%.
Wherein, the weight content T% of mutual-phenenyl two acid bromide two alcohol ester's unit is 35wt%-65wt% in the PBAT resins.
When T% is less than 35wt%, the product made is too soft, is unfavorable for using, and when T% is higher than 65wt%, product is too hard, is unfavorable for using.
Wherein, the shear viscosity of the PBAT resins is less than or equal to 180Pa*s more than 10Pa*s, wherein, shear viscosity
Method of testing is：Using capillary rheometer determining, temperature： 210℃；Capillary diameter：1mm；Capillary pipe length：40mm；Pressure
Force snesor range：200MPa；Test shear rate is 5000s-1.
The present invention also provides the preparation method of above-mentioned PBAT 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, adipic acid is added, 240 DEG C -260 DEG C is warming up to and continues to react 2-4 hours, addition accounts for PBAT 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 PBAT 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 0.61%- in PBAT resins by adding a small amount of isocyanates, and by the content of isocyanates
It in the range of 0.75%, can meet the rheological property of PBAT resins：In shear rate 5000s-1, shear viscosity is more than 10
Pa*s is less than or equal to 180 Pa*s, ensures to be crosslinked while the viscosity for improving PBAT resins ensures blown film stability
Degree, and resin has the blown film characteristic being obviously improved, in fair speed blown film, membrane material obtains good film-forming property, and is not in
The situation of holes and fisheye, it ensure that the continuity of blown film production.
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, adipic acid is added, 240 DEG C -260 DEG C is warming up to and continues to react 2-4 hours, addition accounts for
PBAT 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 PBAT resins.Change terephthaldehyde
The inventory of acid and adipic acid, you can obtain the PBAT 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 PBAT resins of different isocyanate contents.
The PBAT resins being prepared are subjected to blown film by following blown film condition：
Blown film condition：Film blowing machine screw temperature is 135 DEG C, and membrane material thickness is 15 μm, and blown film speed is 175 Kg/h.Test it
Results of property is as shown in table 2.
Table 1
Performance test standard：
Shear viscosity：Using capillary rheometer determining, test condition：Temperature： 210℃；Capillary diameter：1mm；Capillary
Length：40mm；Pressure sensor range：200MPa；Test shear rate is 5000s-1.
Holes situation：Continuous blown film produces 8 hours, film bubble holes number occurs.
Fisheye number：Sample 1m2,（Membrane material thickness is 15 μm）, fisheye of the membrane material surface diameter more than 1mm is observed light
Number；Sample 3 times and take arithmetic average.
Isocyanate weight content assaying method：It is measured using elemental analyser, by 0.1-0.5gPBAT 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 1-6 of table 2 and comparative example 1-4 each components with when the performance test results
From Table 2, it can be seen that when the content of isocyanates is 0.61-0.75% in PBAT resins, the shearing of PBAT resins sticks
Degree is less than or equal to 180Pa*s more than 10Pa*s, ensures to be crosslinked excessively while improving viscosity and ensureing blown film stability, and
Resin has the blown film characteristic that is obviously improved, and in fair speed blown film, membrane material obtains good film-forming property, and be not in holes and
The situation of fisheye, it ensure that the continuity of blown film production.And the content of isocyanates is less than 0.61% or is higher than in comparative example 1-4
When 0.75%, the shear viscosities of PBAT resins is less than 10Pa*s or more than 180Pa*s, and plasticizing is easily caused not in blow-molding process
It is good, there is broken empty and fisheye, influence the performance and blown film continuous production of film.
Claims (6)
- A kind of 1. PBAT resins, it is characterised in that including：（a）Mutual-phenenyl two acid bromide two alcohol ester's unit；（b）Tetramethylene adipate unit；（c）Isocyanates；Wherein, the gross weight based on PBAT resins, the weight content of isocyanates is 0.61%-0.75%.
- A kind of 2. PBAT 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 0.1-0.5gPBAT 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 PBAT resins according to claim 1, it is characterised in that the gross weight based on PBAT resins, isocyanic acid The weight content of ester is 0.65%-0.71%.
- A kind of 4. PBAT resins according to claim 1, it is characterised in that the gross weight based on PBAT resins is described right The weight content T% of benzene dicarboxylic acid butanediol ester unit is 35wt%-65wt%.
- 5. a kind of PBAT resins according to claim any one of 1-4, it is characterised in that the shearing of the PBAT resins sticks Degree is less than or equal to 180Pa*s more than 10Pa*s, wherein, the method for testing of shear viscosity is：Using capillary rheometer determining, survey Strip part：Temperature： 210℃；Capillary diameter：1mm；Capillary pipe length：40mm；Pressure sensor range：200MPa；Test Shear rate is 5000s-1.
- 6. the preparation method of a kind of PBAT resins according to claim any one of 1-5, 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, adipic acid is added, 240 DEG C -260 DEG C is warming up to and continues to react 2-4 hours, addition accounts for PBAT 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 PBAT resins.
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| CN201710531078.XA CN107474230A (en) | 2017-07-03 | 2017-07-03 | A kind of PBAT resins and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102164984A (en) * | 2008-09-29 | 2011-08-24 | 巴斯夫欧洲公司 | Aliphatic-aromatic polyester |
| CN103483522A (en) * | 2012-06-11 | 2014-01-01 | 上海杰事杰新材料(集团)股份有限公司 | High molecular weight aliphatic-aromatic copolyester and preparation method thereof |
| CN104497293A (en) * | 2014-12-01 | 2015-04-08 | 金发科技股份有限公司 | Biodegradable aliphatic-aromatic copolyester and application thereof |
| CN105658728A (en) * | 2013-10-25 | 2016-06-08 | 乐天精密化学株式会社 | Biodegradable polyester resin compound and foam obtained from same |
-
2017
- 2017-07-03 CN CN201710531078.XA patent/CN107474230A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102164984A (en) * | 2008-09-29 | 2011-08-24 | 巴斯夫欧洲公司 | Aliphatic-aromatic polyester |
| CN103483522A (en) * | 2012-06-11 | 2014-01-01 | 上海杰事杰新材料(集团)股份有限公司 | High molecular weight aliphatic-aromatic copolyester and preparation method thereof |
| CN105658728A (en) * | 2013-10-25 | 2016-06-08 | 乐天精密化学株式会社 | Biodegradable polyester resin compound and foam obtained from same |
| CN104497293A (en) * | 2014-12-01 | 2015-04-08 | 金发科技股份有限公司 | Biodegradable aliphatic-aromatic copolyester and application thereof |
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Application publication date: 20171215 |