CN110283312A - A kind of in-situ modified poly (propylene carbonate) of poly-lactam and preparation method thereof - Google Patents
A kind of in-situ modified poly (propylene carbonate) of poly-lactam and preparation method thereof Download PDFInfo
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- CN110283312A CN110283312A CN201811525070.3A CN201811525070A CN110283312A CN 110283312 A CN110283312 A CN 110283312A CN 201811525070 A CN201811525070 A CN 201811525070A CN 110283312 A CN110283312 A CN 110283312A
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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Abstract
The present invention relates to technical field of polymer materials, poor for the thermostability of propylene carbonate of the prior art, the low problem of intensity, disclose a kind of in-situ modified poly (propylene carbonate) of poly-lactam and preparation method thereof.The in-situ modified poly (propylene carbonate) of poly-lactam is made of lactam monomers, end-capping reagent and poly (propylene carbonate) by in-situ polymerization.The present invention first carries out chemical blocking modification to poly (propylene carbonate) with isocyanates, maleic anhydride isoreactivity end-capping reagent, is copolymerized under certain condition with third component compound again later, to obtain the in-situ modified poly (propylene carbonate) of poly-lactam.The glass transition temperature of modification poly (propylene carbonate) of the invention improves 10 ~ 100 DEG C, and thermal decomposition temperature improves 10 ~ 50 DEG C, and mechanical property improves 10 ~ 80%, and preparation method is simple, is suitble to large-scale production.
Description
Technical field
The present invention relates to technical field of polymer materials more particularly to a kind of in-situ modified poly (propylene carbonate)s of poly-lactam
And preparation method thereof.
Background technique
Since twentieth century, with the development of science and technology, more and more plastic products are manufactured, give us with next life
It is living convenient simultaneously as its major part is non-degradable material and brings serious " white pollution " and greenhouse effects, with
The also strong influence mankind physical and mental health.Therefore develop Biodegradable material and reduce greenhouse effects problem and compel in eyebrow
Eyelash.Poly (propylene carbonate) (PPC) is by carbon dioxide and propylene oxide in certain catalyst and certain pressure, temperature strip
A kind of Novel environment-friendlymaterial material for the fully biodegradable polymerizeing under part, and be original using GHG carbon dioxide
Material, can reduce environmental pollution caused by white pollution and greenhouse effects simultaneously, have apparent application prospect.But PPC
Thermal stability is poor, and intensity is low, significantly limits it in the application of the industries such as plastics, chemical industry.Researcher is to its warm at present
Improved stability has carried out extensive research.It is presently mainly hot to improve its by way of conventional solution or melt blending
Energy.
The patent of Chinese patent application Publication No. CN107573476A discloses a kind of modified poly (propylene carbonate) material
Preparation method, including will poly (propylene carbonate) be added solvent in be completely dissolved, then be added anhydride end-capping reagent, in a water bath
Heating reaction；The reaction was continued after raising temperature addition isocyanates end-capping reagent；The mixture of fully reacting is added drop-wise to anhydrous
Precipitation is carried out in ethyl alcohol, is dried in vacuo after obtained solid is filtered.The method increase the vitrifyings of poly (propylene carbonate)
Transition temperature and thermal stability, but its promotion effect is not fairly obvious.State's patent application publication number is CN108164978A,
The patent of CN107474502A, CN105924923A also illustrate poly (propylene carbonate) modification, but modified effect is not
It is obvious that and since there are the consistency problems of component of mixture, also can to modified effect generate significantly affect.It uses at present
Some researchs of chemical method MODIFIED PP C are reported in media every now and then, but do not go deep into systematic research mostly and carry out to have
The application of effect.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of in-situ modified poly (propylene carbonate) of poly-lactam and its
Preparation method.The hot property and mechanical property of the in-situ modified poly (propylene carbonate) of poly-lactam of the invention be improved significantly,
Compared with unmodified poly (propylene carbonate), the glass transition temperature of the in-situ modified poly (propylene carbonate) of the poly-lactam is improved
60℃；Thermal decomposition temperature improves 40 DEG C；Mechanical property improves 70%.
The specific technical proposal of the invention is: a kind of in-situ modified poly (propylene carbonate) of poly-lactam, the poly-lactam
In-situ modified poly (propylene carbonate) is made of lactam monomers, end-capping reagent and poly (propylene carbonate) by in-situ polymerization.
The invention is mainly technically characterized by sealing by chemical method using such as isocyanates, maleic anhydride isoreactivity
It holds agent to carry out chemical blocking modification to poly (propylene carbonate), is total under certain condition with third component compound again later
It is poly-, to obtain the in-situ modified poly (propylene carbonate) of poly-lactam.
Because the thermal stability of poly (propylene carbonate) is bad, reason is to occur randomly to be broken and generate when it is heated
Oligomer, and solution zip mode degradation easily occurs due to the presence of poly (propylene carbonate) terminal hydroxy group, when being heated, and every time
Next cricoid propene carbonate is taken off in poly (propylene carbonate) end.It therefore, need to be to its terminal hydroxy group to improve its thermal stability
Carry out blocking modification.The relative density of poly-lactam class material is small, intensity is high, stability is good, wearability is good, long-term use temperature
It is higher, and can be reacted with the group on poly (propylene carbonate) end-capping reagent.Therefore the present invention selects poly-lactam class monomer to make
For the Third monomer of modified poly (propylene carbonate).Due to poly-lactam not easily biological-degradable, therefore, it is necessary to strict control it is poly- in acyl
The dosage of amine monomers.Combined polymerization is carried out using lactams and isocyanate-terminated poly (propylene carbonate), thus in molecule knot
Chemical modification is carried out to poly (propylene carbonate) on structure, the composite material of excellent mechanical performances and hot property is obtained, to make poly- carbon
The application field of sour Asia propyl ester material is expanded and extend.
Preferably, the molar ratio of the poly (propylene carbonate) terminal hydroxyl and end-capping reagent and lactam monomers be 1:1~
5:0.05~0.5.
As previously mentioned, the thermal stability of poly (propylene carbonate) is bad, to improve this problem, its terminal hydroxy group need to be sealed
End is modified.Moreover, carrying out copolyreaction in view of then needing to add third component, isocyanates must be excessive, by repeatedly real
It tramples, the molar ratio of isocyanates and poly (propylene carbonate) end OH is advisable between 1.0~5.0.In view of poly (propylene carbonate) material
Degradability, the content of the Third monomer polyamide component of addition should not be too high.By repeatedly practicing, by lactam monomers
Content is determined as 1.0~20.0% (in terms of the molal quantitys of poly (propylene carbonate)).
Preferably, the molecular weight of the poly (propylene carbonate) is 1000~20000.Because poly (propylene carbonate) is a kind of
The Novel environment-friendlymaterial material of fully biodegradable, molecular weight should not be too big, and too big degradation is slowly, too small not have intensity, can not
It uses.
Preferably, the end-capping reagent is diisocyanates or maleic anhydride, the diisocyanates include toluene
2,4- diisocyanate, two isocyanide of hexamethylene diisocyanate, 4,4'- dicyclohexyl methyl hydride diisocyanate and diphenyl-methane
At least one of acid esters.Preferably, the lactam monomers include in caprolactam, caprinolactam and lauric lactam
It is at least one.
It further include modified mulberry tree fiber in the in-situ modified poly (propylene carbonate) of poly-lactam；The modified mulberry tree fiber
Additional amount be poly (propylene carbonate) quality 0.5~1.5%.Preferably, the modified mulberry tree fiber the preparation method comprises the following steps:
The mulberry tree fiber that diameter is 20~30nm is placed in closed container, liquefied ammonia is filled with, is 0.6~1MPa/min's with rate of pressure rise
Rate of pressure rise rises to 2~3MPa of pressure, then by rate of pressure rise boosting 2~3min, the 5~7min of pressure maintaining of 0.6~1MPa/min, so
The mulberry of crystal change modification is obtained with the rate of pressure reduction abrupt release of 4~5MPa/s to 0.005~0.008MPa in 1.5~2 seconds afterwards
Set fiber.The mulberry tree fiber of crystal change modification is placed in hydrothermal reaction kettle, in 160~200 DEG C of 40~70min of hydrothermal carbonization, mistake
Carbon fiber is obtained after filter, washing, drying.Using obtained carbon fiber as anode, using graphite as cathode, the carbon for being 4~7% in concentration
1~1.5min is aoxidized in acid ammonium solution under conditions of current strength is 0.8~1A, obtains carbon oxide fiber.The oxygen that will be obtained
Change the dispersion liquid that carbon fiber is dispersed into 2~5mg/mL, aminopropyl trimethoxysilane, the modified carbon of graphene oxide enhancing is added
Fiber and the mass ratio of aminopropyl trimethoxysilane are 1~3:1, obtain modified mulberry tree fiber in 60~80 DEG C of 4~6h of reaction.
The intensity of mulberry tree fiber is high, good toughness, but wearability and poor, this implementation with the compatibility of poly (propylene carbonate)
Example becomes mulberry tree fibrous crystal, improves its swellability, and then carbon fiber is made in carbonization, improves the wearability of mulberry tree fiber, then right
It carries out oxidation processes, increases the quantity of the active function groups on its surface, is finally modified with organosiloxane to it, increases
The compatibility of itself and poly (propylene carbonate).Modified mulberry tree fiber can be with the isocyanates in hexamethylene diisocyanate
Amino crosslinking in base and lauric lactam, increases the intensity and wearability of silanization poly (propylene carbonate).Due to modified
Mulberry tree fiber is dispersed in silanization poly (propylene carbonate), and is crosslinked combination by chemical bond, fine with unmodified mulberry tree
Dimension is compared, and the compatibility of modified mulberry tree fiber and poly (propylene carbonate) is good, and surface group can be with poly (propylene carbonate) and envelope
The functional groups in agent are held, the thermal stability and mechanical strength of poly (propylene carbonate) can be significantly increased.
A kind of preparation method of the in-situ modified poly (propylene carbonate) of poly-lactam, comprising the following steps:
(1) chemistry sealing end: poly (propylene carbonate) is sufficiently mixed with end-capping reagent in proportion, side in pyroreaction kettle is subsequently placed in and stirs
It mixes side and carries out melt blending, obtain the poly (propylene carbonate) of chemistry sealing end；
(2) in-situ polymerization: lactams is proportionally added into the reaction kettle in step (1), the polymerized thylene carbonate with chemistry sealing end
Propyl ester carries out copolymerization, arrives the in-situ modified poly (propylene carbonate) of poly-lactam to discharging check rod pelletizing.
Utilize the in-situ modified poly (propylene carbonate) of poly-lactam made from method of the invention and unmodified polymerized thylene carbonate
Propyl ester is compared, and glass transition temperature improves 10~100 DEG C, and thermal decomposition temperature improves 10~50 DEG C, and mechanical property improves 10
~80%.Heat resistance and mechanical property are obviously improved, and the comprehensive performance of modified poly (propylene carbonate) is substantially improved, effectively
Widen the application field of poly (propylene carbonate) in ground.
Preferably, in step (1), the poly (propylene carbonate) dry 8~12h under the conditions of 30~40 DEG C；Melting is altogether
Mixed temperature is 50~200 DEG C, and the time is 2~12h.Preferably, the melt blending temperature is 100~200 DEG C, the time 2
~10h.
Preferably, the polymerization temperature is 100~220 DEG C, 0.5~6h of reaction time in step (2).
Compared with prior art, the invention has the following advantages: the present invention mainly passes through chemical method, utilization is all
If isocyanates, maleic anhydride isoreactivity end-capping reagent carry out chemical blocking modification to poly (propylene carbonate), later again with third group
Point compound is copolymerized under certain condition, and traditional to obtain poly (propylene carbonate)/polymer copolymerization composite material
It is significantly different by physical modification method.This patent is using in-situ polymerization technique, i.e., by the poly- carbon of activating agent sealing end
Sour Asia propyl ester is directly mixed with the melt of third component monomer, after under specific polymerization technique progress polymeric modification and answered
Condensation material, by testing after tested, the hot property and mechanical property of the in-situ modified poly (propylene carbonate) of the poly-lactam obtain bright
It is aobvious to improve, compared with unmodified poly (propylene carbonate), the glass transition of the in-situ modified poly (propylene carbonate) of the poly-lactam
Temperature improves 60 DEG C, and thermal decomposition temperature improves 40 DEG C, and mechanical property improves 70%, makes the application field of poly (propylene carbonate) material
It is expanded and extend.
Specific embodiment
The present invention will be further described with reference to the examples below.Related device, connection structure in the present invention
And method, if being device well known in the art, connection structure and method without refering in particular to.
Embodiment 1
A kind of preparation method of the in-situ modified poly (propylene carbonate) of poly-lactam, comprising the following steps:
(1) chemistry sealing end: according to poly- carbon after dry 12h under the conditions of being 35 DEG C of poly (propylene carbonate) of 20000 by 100g molecular weight
The ratio and '-diphenylmethane diisocyanate that the molar ratio of sour Asia propyl ester terminal hydroxyl and '-diphenylmethane diisocyanate is 1:2.5
It is sufficiently mixed, is subsequently placed in pyroreaction kettle while stirring in 150 DEG C of melt blending 6h, obtains the polymerized thylene carbonate of chemistry sealing end
Propyl ester；
(2) in-situ polymerization: by the dry caprolactam of 0.57g rubbing according to poly (propylene carbonate) terminal hydroxyl and caprolactam monomer
That is total at 170 DEG C with the poly (propylene carbonate) of chemistry sealing end than being that the ratio of 1:0.5 is added in the reaction kettle in step (1)
Polymerization reaction 1h arrives the in-situ modified poly (propylene carbonate) of polycaprolactam to discharging check rod pelletizing.
Embodiment 2
A kind of preparation method of the in-situ modified poly (propylene carbonate) of poly-lactam, comprising the following steps:
(1) chemistry sealing end: by 100g molecular weight be 10000 poly (propylene carbonate) after 30 DEG C of dry 12h according to polymerized thylene carbonate
The ratio and 2.8g '-diphenylmethane diisocyanate that the molar ratio of propyl ester terminal hydroxyl and '-diphenylmethane diisocyanate is 1:1.6
It is sufficiently mixed, is subsequently placed in pyroreaction kettle while stirring in 130 DEG C of melt blending 8h, obtains the polymerized thylene carbonate of chemistry sealing end
Propyl ester；
(2) in-situ polymerization: by 0.79g dry lauric lactam according to poly (propylene carbonate) terminal hydroxyl and lauric lactam list
The molar ratio of body is that the ratio of 1:0.2 is added in the reaction kettle in step (1), is existed with the poly (propylene carbonate) of chemistry sealing end
170 DEG C of copolymerization 1h arrive the in-situ modified poly (propylene carbonate) of nylon 12 to discharging check rod pelletizing.
Embodiment 3
A kind of preparation method of the in-situ modified poly (propylene carbonate) of poly-lactam, comprising the following steps:
(1) chemistry sealing end: by 100g molecular weight be 4000 poly (propylene carbonate) after 35 DEG C of dry 8h according to polymerized thylene carbonate third
The molar ratio of ester terminal hydroxyl and toluene 2,4- diisocyanate is that the ratio of 1:1.1 is filled with 4.8g toluene 2,4- diisocyanate
Divide mixing, is subsequently placed in pyroreaction kettle while stirring in 100 DEG C of melt blending 10h, obtains the polymerized thylene carbonate of chemistry sealing end
Propyl ester；
(2) in-situ polymerization: by the dry caprolactam of 0.3g rubbing according to poly (propylene carbonate) terminal hydroxyl and caprolactam monomer
That is total at 130 DEG C with the poly (propylene carbonate) of chemistry sealing end than being that the ratio of 1:0.05 is added in the reaction kettle in step (1)
Polymerization reaction 3h arrives the in-situ modified poly (propylene carbonate) of polycaprolactam to discharging check rod pelletizing.
Embodiment 4
A kind of preparation method of the in-situ modified poly (propylene carbonate) of poly-lactam, comprising the following steps:
(1) chemistry sealing end: by 100g molecular weight be 10000 poly (propylene carbonate) after 30 DEG C of dry 12h according to polymerized thylene carbonate
The ratio and 2.8g hexamethylene diisocyanate that the molar ratio of propyl ester terminal hydroxyl and hexamethylene diisocyanate is 1:1.6
It is sufficiently mixed, is subsequently placed in pyroreaction kettle while stirring in 130 DEG C of melt blending 8h, obtains the polymerized thylene carbonate of chemistry sealing end
Propyl ester；
(2) in-situ polymerization: by 0.79g dry lauric lactam according to poly (propylene carbonate) terminal hydroxyl and lauric lactam list
The molar ratio of body is that the ratio of 1:0.2 is added in the reaction kettle in step (1), and poly (propylene carbonate) quality is then added
0.5% times of modification mulberry tree fiber, the poly (propylene carbonate) with chemistry sealing end is in 100 DEG C of copolymerization 6h, to discharging check rod
Pelletizing to get arrive the in-situ modified poly (propylene carbonate) of nylon 12.
Wherein, modified mulberry tree fiber the preparation method comprises the following steps: the mulberry tree fiber that diameter is 20nm is placed in closed container, fill
Enter liquefied ammonia, the rate of pressure rise with rate of pressure rise for 1MPa/min rises to pressure 3MPa, then boosts by the rate of pressure rise of 1MPa/min
2min, pressure maintaining 5min, then the rate of pressure reduction abrupt release in 1.5 seconds with 4MPa/s obtains crystal change modification to 0.005MPa
Mulberry tree fiber.The mulberry tree fiber of crystal change modification is placed in hydrothermal reaction kettle, in 200 DEG C of hydrothermal carbonization 40min, filters, wash
Wash, dry after obtain carbon fiber.Using obtained carbon fiber as anode, using graphite as cathode, the sal volatile for being 7% in concentration
In current strength be 1A under conditions of aoxidize 1min, obtain carbon oxide fiber.Obtained carbon oxide fiber is dispersed into 4mg/
Aminopropyl trimethoxysilane, graphene oxide enhancing modified carbon fiber and aminopropyl trimethoxy is added in the dispersion liquid of mL
The mass ratio of silane is 2:1, obtains modified mulberry tree fiber in 80 DEG C of reaction 4h.
Comparative example 1
Comparative example 1 difference from example 1 is that: only with '-diphenylmethane diisocyanate to poly (propylene carbonate)
Sealing end is learned, without the home position polymerization reaction of step (2), other are same as Example 1.
Comparative example 2
Comparative example 2 difference from example 1 is that:, will be dry under the conditions of 35 DEG C of poly (propylene carbonate) in step (1)
The ratio and hexichol for being 1:2.5 according to the molar ratio of poly (propylene carbonate) terminal hydroxyl and '-diphenylmethane diisocyanate after 12h
Methane diisocyanate is sufficiently mixed, other are same as Example 1.
Comparative example 3
Comparative example 3 and embodiment 4 the difference is that: replaces modification mulberry tree fiber with unmodified mulberry tree fiber, other are equal
It is same as Example 4.
To the in-situ modified poly (propylene carbonate) of poly-lactam made from Examples 1 to 4 and comparative example 1~3 and blank group
Glass transition temperature, thermal decomposition temperature and the breaking strength of unmodified poly (propylene carbonate) are detected, and test result is shown in
Table 1.
Table 1
As can be seen from Table 1, the glass transition temperature of the in-situ modified poly (propylene carbonate) of poly-lactam of the invention, thermal decomposition
Temperature and mechanical property are significantly improved.Compared to unmodified poly (propylene carbonate), poly- 12 made from embodiment 1 in acyl
The glass transition temperature of the in-situ modified poly (propylene carbonate) of amine improves 50 DEG C, and thermal decomposition temperature improves 40 DEG C, and mechanical property mentions
It is high by 70%.Compared with being modified poly (propylene carbonate) made from comparative example 1~2, nylon 12 made from embodiment 1 changes in situ
Glass transition temperature, thermal decomposition temperature and the mechanical property of property poly (propylene carbonate) also increase significantly.Illustrate merely
Sealing end is carried out to poly (propylene carbonate) or the amount of end-capping reagent is very few in sealing end is all unfavorable for modified poly (propylene carbonate) performance
It improves.To be modified mulberry tree fiber as reinforcing material in embodiment 4, the in-situ modified poly (propylene carbonate) of poly-lactam obtained
Glass transition temperature, thermal decomposition temperature and mechanical property are significantly improved.Comparative example 3 compared with Example 4, comparative example 3
Glass transition temperature, thermal decomposition temperature and the mechanical property and implementation of the in-situ modified poly (propylene carbonate) of poly-lactam obtained
Example 4, which is compared, has very big gap, the reason is that, the poor compatibility of unmodified mulberry tree fiber and poly (propylene carbonate), mulberry tree
Fiber disperses the thermal decomposition temperature and fracture that unevenly lead to silanization poly (propylene carbonate) obtained in poly (propylene carbonate)
Intensity is poor, or even the thermal stability of while not adding mulberry tree fiber not as good as embodiment 2 silanization poly (propylene carbonate) obtained
With breaking strength height.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent structure transformation to the above embodiments, still fall within skill of the present invention
The protection scope of art scheme.
Claims (9)
1. a kind of in-situ modified poly (propylene carbonate) of poly-lactam, it is characterised in that: the in-situ modified poly- carbonic acid of poly-lactam
Sub- propyl ester is made of lactam monomers, end-capping reagent and poly (propylene carbonate) by in-situ polymerization.
2. the in-situ modified poly (propylene carbonate) of a kind of poly-lactam according to claim 1, it is characterised in that: the poly- carbon
The molar ratio of sour Asia propyl ester terminal hydroxyl and end-capping reagent and lactam monomers is 1:1 ~ 5:0.05 ~ 0.5.
3. the in-situ modified poly (propylene carbonate) of a kind of poly-lactam according to claim 2, it is characterised in that: the poly- carbon
The molecular weight of sour Asia propyl ester is 1000~20000.
4. the in-situ modified poly (propylene carbonate) of a kind of poly-lactam according to claim 2, it is characterised in that: the sealing end
Agent is diisocyanates or maleic anhydride, and the diisocyanates include toluene 2,4- diisocyanate, hexa-methylene two
At least one of isocyanates, 4,4'- dicyclohexyl methyl hydride diisocyanate and '-diphenylmethane diisocyanate；The interior acyl
Amine monomers include at least one of caprolactam, caprinolactam and lauric lactam.
5. the in-situ modified poly (propylene carbonate) of a kind of poly-lactam according to claim 1, it is characterised in that: described poly- interior
It further include modified mulberry tree fiber in the in-situ modified poly (propylene carbonate) of amide；The additional amount of the modified mulberry tree fiber is poly- carbonic acid
The 0.5 ~ 1.5% of sub- propyl ester quality.
6. a kind of preparation method of the in-situ modified poly (propylene carbonate) of poly-lactam any according to claim 1 ~ 5,
Be characterized in that the following steps are included:
(1) chemistry sealing end: poly (propylene carbonate) is sufficiently mixed with end-capping reagent in proportion, is subsequently placed in reactor while stirring
Melt blending is carried out, the poly (propylene carbonate) of chemistry sealing end is obtained；
(2) in-situ polymerization: lactams is proportionally added into the reactor in step (1), the polymerized thylene carbonate with chemistry sealing end
Propyl ester carries out copolymerization, arrives the in-situ modified poly (propylene carbonate) of poly-lactam to discharging check rod pelletizing.
7. a kind of preparation method of the in-situ modified poly (propylene carbonate) of poly-lactam according to claim 6, feature exist
In: in step (1), the poly (propylene carbonate) dry 8 ~ 12h under the conditions of 30 ~ 40 DEG C；Melt blending temperature is 50~200
DEG C, the time is 2~12h.
8. a kind of preparation method of the in-situ modified poly (propylene carbonate) of poly-lactam according to claim 7, feature exist
In: the frit reaction temperature is 100~200 DEG C, and the time is 2~10h.
9. a kind of preparation method of the in-situ modified poly (propylene carbonate) of poly-lactam according to claim 6, feature exist
In: in step (2), the polymerization temperature is 100~220 DEG C, 0.5~6h of reaction time.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261260A (en) * | 2010-12-28 | 2013-08-21 | Sk新技术株式会社 | Method for improving thermal stability of polypropylene carbonate |
| CN104479081A (en) * | 2015-01-14 | 2015-04-01 | 河北工业大学 | Method for modifying polypropylene carbonate through reaction extrusion |
| CN105176035A (en) * | 2015-08-10 | 2015-12-23 | 河南大学 | Nylon powder / poly propylene carbonate composite material and preparation method thereof |
| CN107573476A (en) * | 2016-07-05 | 2018-01-12 | 中国石油化工股份有限公司 | The preparation method of modified poly (propylene carbonate) material |
| CN107868425A (en) * | 2017-10-12 | 2018-04-03 | 杭州师范大学 | A kind of high-performance polymethyl ethylene carbonate material and preparation method thereof |
| CN108047678A (en) * | 2017-12-15 | 2018-05-18 | 武汉工程大学 | A kind of modified lignin resin/polypropylene carbonate composite material and preparation method thereof |
| CN108603020A (en) * | 2016-05-31 | 2018-09-28 | Lg化学株式会社 | Polymerized thylene carbonate alkyl ester resin combination, preparation method, the moulding article of formation and the preparation method using its moulding article |
-
2018
- 2018-12-13 CN CN201811525070.3A patent/CN110283312B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261260A (en) * | 2010-12-28 | 2013-08-21 | Sk新技术株式会社 | Method for improving thermal stability of polypropylene carbonate |
| CN104479081A (en) * | 2015-01-14 | 2015-04-01 | 河北工业大学 | Method for modifying polypropylene carbonate through reaction extrusion |
| CN105176035A (en) * | 2015-08-10 | 2015-12-23 | 河南大学 | Nylon powder / poly propylene carbonate composite material and preparation method thereof |
| CN108603020A (en) * | 2016-05-31 | 2018-09-28 | Lg化学株式会社 | Polymerized thylene carbonate alkyl ester resin combination, preparation method, the moulding article of formation and the preparation method using its moulding article |
| CN107573476A (en) * | 2016-07-05 | 2018-01-12 | 中国石油化工股份有限公司 | The preparation method of modified poly (propylene carbonate) material |
| CN107868425A (en) * | 2017-10-12 | 2018-04-03 | 杭州师范大学 | A kind of high-performance polymethyl ethylene carbonate material and preparation method thereof |
| CN108047678A (en) * | 2017-12-15 | 2018-05-18 | 武汉工程大学 | A kind of modified lignin resin/polypropylene carbonate composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| WU HAI-LIANG等: "Research on the Structure and Properties of Mulberry Fiber", 《JOURNAL OF DONGHUA UNIVERSITY》 * |
| 唐见茂: "《绿色复合材料》", 31 December 2016 * |
| 孙娇等: "聚碳酸亚丙酯化学改性研究进展", 《中国印刷与包装研》 * |
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