CN106008931A - PBS/basic magnesium sulfate whisker composite and preparation method - Google Patents
PBS/basic magnesium sulfate whisker composite and preparation method Download PDFInfo
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- CN106008931A CN106008931A CN201610411219.XA CN201610411219A CN106008931A CN 106008931 A CN106008931 A CN 106008931A CN 201610411219 A CN201610411219 A CN 201610411219A CN 106008931 A CN106008931 A CN 106008931A
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- magnesium sulfate
- sulfate crystal
- crystal whisker
- pbs
- alkali magnesium
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 title claims abstract description 178
- 229910052943 magnesium sulfate Inorganic materials 0.000 title claims abstract description 89
- 235000019341 magnesium sulphate Nutrition 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 41
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000001384 succinic acid Substances 0.000 claims abstract description 20
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 16
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims description 81
- 239000013078 crystal Substances 0.000 claims description 77
- 239000003054 catalyst Substances 0.000 claims description 13
- 150000002118 epoxides Chemical class 0.000 claims description 7
- 239000004033 plastic Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 238000005452 bending Methods 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- ZGBSOTLWHZQNLH-UHFFFAOYSA-N [Mg].S(O)(O)(=O)=O Chemical compound [Mg].S(O)(O)(=O)=O ZGBSOTLWHZQNLH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002808 molecular sieve Substances 0.000 abstract description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011159 matrix material Substances 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 238000006735 epoxidation reaction Methods 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
- 238000009835 boiling Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 229910000077 silane Inorganic materials 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention provides a PBS/basic magnesium sulfate whisker composite and a preparation method. The preparation method includes the steps that firstly, the surfaces of basic magnesium sulfate whiskers are modified with KH560 to form epoxidized basic magnesium sulfate whiskers; then, the epoxidized basic magnesium sulfate whiskers, succinic acid and butanediol are subjected to in-situ polycondensation under the catalysis of a titanium-silicon molecular sieve to prepare the PBS/basic magnesium sulfate whisker composite. After the basic magnesium sulfate whiskers used in the method are subjected to epoxidation modification, surface lipophilicity is substantially improved, epoxy groups carried by the epoxidized basic magnesium sulfate whiskers have high reactivity with carboxyl of succinic acid and hydroxyl of butanediol, and thus in-situ polymerization preparation of the PBS/basic magnesium sulfate whisker composite is easy. The thermal performance and technical performance of the obtained composite are obviously improved, and the problems that at present, PBS is high in brittleness and poor in thermal performance, and the compatibility of basic magnesium sulfate whiskers and a resin matrix is poor are solved.
Description
Technical field
The present invention relates to Biodegradable material field, particularly to a kind of PBS/ alkali magnesium sulfate crystal whisker composite and preparation side
Method.
Background technology
Along with developing rapidly of plastics industry, the macromolecular material of synthesis instead of traditional metal, glass, wood in various fields
The materials such as material, especially at packaging industry, apply and extensive.But, a large amount of due to cutlery box, packaging bag and disposable garbage bag
Using and cause serious " white pollution " problem, the development and application of Biodegradable material increasingly causes the concern of people.
PBS is the aliphatic polyester that a kind of comprehensive comparison is excellent, has heat-resisting a, resistance to chemical attack, and easy machining is excellent
Biocompatibility and fully biodegradable performance.It is in anaerobics such as compost, sea water, the moist earth having germs collect or has
Can be degradable for non-toxic products such as water, carbon dioxide or biogas in the environment of oxygen.But, it is relatively big that PBS there is also fragility, intensity
Relatively low, relatively costly, and the defect such as inorganic filler poor compatibility, these drawbacks limit large-scale application of PBS.Therefore, PBS
Modification become the study hotspot of current degradable polyester.
Alkali magnesium sulfate crystal whisker (MgSO4·5Mg(OH)2·3H2O) it is the mono-crystlling fibre material of a kind of high intensity, high elastic modulus,
Can be used as the additive of plastics, rubber etc., improve flexural strength and the impulsive force of matrix material, its coefficient of expansion is close simultaneously
Plastics the therewith compatibility are good, show excellent physical and mechanical property.Alkali magnesium sulfate crystal whisker nontoxic, the amount of being fuming is little, resistance
Combustion property is good and lower-price characteristic makes it can be used for preparing composite, while being greatly improved the properties of composite also
The production cost of matrix material can be reduced.
At present the modified of PBS are used the simple method being blended or add the 3rd component copolymerization more.Patent [CN 104861594 A] is made
Standby PBS/CaCO3Composite have employed simple doped and compounded, will PBS, CaCO3Filler, coupling agent, antioxidation
Agent and other auxiliary agent mix banburying, extruding pelletization in melt blending mode together；Alkali formula sulfur prepared by patent [CN 105017765 A]
Acid magnesium whisker/PA610T composites is to add double screw extruder extruding pelletization, dry after raw material and various auxiliary agent mix homogeneously
Dry, injection mo(u)lding.But this type of modification must be higher to equipment requirements by various raw material height mix homogeneously, inorganic material even across
Modified the most difficult and polymeric matrix reaches the highest compatibility, additionally, interpolation compatilizer, lubricant, antioxidant cause cost
Higher.The present invention is to be modified with the alkali magnesium sulfate crystal whisker of epoxide group in the addition of PBS building-up process, uses the side of in-situ polymerization
Method prepares PBS/ alkali magnesium sulfate crystal whisker composite, and its mechanical property and heat stability significantly improve.
Summary of the invention
In order to overcome the problems referred to above, the present invention fills a kind of epoxidation alkali magnesium sulfate crystal whisker in PBS, can reduce PBS's
While production cost, improve its intensity, further expand its application.PBS/ alkali magnesium sulfate crystal whisker composite is complete simultaneously
Required magnesium elements can be provided for the growth of plant because of its distinctive magnesium salt whisker and neutralize modified acid ground after biodegradation.
In order to prepare the degradation plastic of high intensity, the present invention proposes to compound PBS, alkali magnesium sulfate crystal whisker, and utilizes
The two is merged by the home position polymerization reaction of PBS, to avoid using the mechanical forming method higher to equipment requirements, minimizing simultaneously
Learn the interpolation of auxiliary agent.But test result indicate that: add the PBS/ alkali magnesium sulfate crystal whisker that unmodified alkali magnesium sulfate crystal whisker obtains
Mechanical property can not produce a desired effect, it is impossible to meets the mechanical requirements of high intensity.To this end, the present invention is existing to alkali magnesium sulfate crystal whisker
The in-situ polymerization mechanism of some surface modifying methods and modified alkali magnesium sulfate crystal whisker and PBS has carried out systematic study, accidentally sends out
Existing: it is good with succinic acid, the butanediol compatibility in the esterification reaction to be modified with the alkali magnesium sulfate crystal whisker of epoxide group, and can be with
The carboxyl of succinic acid and the hydroxyl reaction of butanediol, thus participate in the polyreaction of PBS.Through the PBS/ that in-situ polymerization prepares
Alkali magnesium sulfate crystal whisker composite, whisker is more traditional in polymeric matrix to be mixed wiping mixing and is uniformly dispersed, and with polymer base
The adhesion of body is relatively strong, can obtain intended mechanical property and heat stability, the PBS/ alkali magnesium sulfate crystal whisker composite obtained
Hot strength reach 46.3Mpa；Bending strength reaches 44.1Mpa.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of PBS/ alkali magnesium sulfate crystal whisker composite, is former with epoxidised alkali magnesium sulfate crystal whisker, succinic acid and butanediol
Material, under catalyst existence condition, in-situ polycondensation forms.
Preferably, the hot strength of described composite is 36.5～46.3Mpa；Bending strength is 29.4～44.1Mpa.
Preferably, the mass ratio of described epoxidised alkali magnesium sulfate crystal whisker, succinic acid and butanediol is 5～15:118:108～126.
Preferably, described epoxidised alkali magnesium sulfate crystal whisker is obtained through silane coupler KH560 modification by alkali magnesium sulfate crystal whisker.
Present invention also offers the preparation method of a kind of PBS/ alkali magnesium sulfate crystal whisker composite, including:
The surface of alkali magnesium sulfate crystal whisker is carried out epoxide modified, obtains epoxidised alkali magnesium sulfate crystal whisker；
With epoxidised alkali magnesium sulfate crystal whisker, succinic acid and butanediol as raw material, carry out contracting in situ under catalyst existence condition
Poly-, to obtain final product.
Preferably, described epoxide modified modifying agent is silane coupler KH560.
Preferably, the mass ratio of described epoxidised alkali magnesium sulfate crystal whisker, succinic acid and butanediol is 5～15:118:108～126.
Preferably, consumption is alkali magnesium sulfate crystal whisker quality the 3～7% of described silane coupler KH560.
Present invention also offers the preparation method of a kind of preferably PBS/ alkali magnesium sulfate crystal whisker composite, concrete preparation method is such as
Under:
Alkali magnesium sulfate crystal whisker processes (see Fig. 1) through silane coupler surface, and whisker with the mass volume ratio of distilled water is
1g:25ml, comprises the following steps: taking a certain amount of distilled water in conical flask, regulating its pH with acetic acid is 4～5, adds whisker
The 3 of quality～the silane coupler (KH560) of 7%, hydrolyze 100～120min in room temperature heat-collecting magnetic stirring device magnetic agitation
After, add a certain amount of whisker and distilled water, then after 20～50 DEG C of magnetic agitation modified 80～100min, sucking filtration, 80 DEG C of bakings
It is standby that dry loading seals bag.
By succinic acid that mol ratio is 1:1.2～1.4 and butanediol, account for the titanium-silicon molecular sieve catalyst of butanediol molal weight 0.1%,
Together add in four-hole boiling flask, 150～180 DEG C of esterifications through the modified alkali magnesium sulfate crystal whisker crossed of silane coupler (KH560)
3h, is warming up to 220 DEG C of polycondensation 5h again after terminating.
After polycondensation reaction terminates, immediately the product in flask is poured in the rectangular disk obtained with made with aluminum foil in advance, be cooled to room temperature, system
Obtain PBS/ alkali magnesium sulfate crystal whisker composite.
Present invention also offers PBS/ alkali magnesium sulfate crystal whisker composite prepared by arbitrary above-mentioned method.
Degradation plastic, rubber or its additive prepared by arbitrary above-mentioned PBS/ alkali magnesium sulfate crystal whisker composite all have relatively
Excellent effect, meets the international standard of relevant industries.
Beneficial effects of the present invention:
1. the present invention adds a kind of epoxidation alkali magnesium sulfate crystal whisker in PBS building-up process, and whisker epoxide group can synthesize with PBS
Raw material succinic acid and butanediol reaction, thus in-situ polycondensation obtains PBS/ alkali magnesium sulfate crystal whisker composite.Reducing PBS
Production cost while, improve its intensity, further expand its application.PBS/ alkali magnesium sulfate crystal whisker composite is complete simultaneously
Required magnesium elements can be provided for the growth of plant because of its distinctive magnesium salt whisker and neutralize modified acid ground after complete biodegradable.
Preparation method the most of the present invention is simple and convenient to operate, practical.
Accompanying drawing explanation
Fig. 1 is the process route chart that alkali magnesium sulfate crystal whisker of the present invention is modified.
Fig. 2 is the TGA curve chart after the present invention adds whisker.
Fig. 3 is PBS/ alkali magnesium sulfate crystal whisker composite median surface of the present invention adhesion condition figure, and wherein, a, b are respectively and do not change
Property (a) and the PBS/ alkali magnesium sulfate crystal whisker composite median surface adhesion condition of modified (b).
Detailed description of the invention
Below in conjunction with instantiation, the invention will be further described.
In the examples below, following method of testing is used:
Tension test is tested by GB GB/T1024.2 2006, test speed 50mm/min, carries out under room temperature.
Bend test is tested by GB GB/T934 2008, test speed 2mm/min, carries out under room temperature.
Alkali magnesium sulfate crystal whisker processes (see Fig. 1) through silane coupler surface, and whisker with the mass volume ratio of distilled water is
1g:25ml, comprises the following steps: taking a certain amount of distilled water in conical flask, regulating its pH with acetic acid is 4～5, adds whisker
The 3 of quality～the silane coupler (KH560) of 7%, hydrolyze 100～120min in room temperature heat-collecting magnetic stirring device magnetic agitation
After, add a certain amount of whisker and distilled water, then after 20～50 DEG C of magnetic agitation modified 80～100min, sucking filtration, 80 DEG C of bakings
It is standby that dry loading seals bag.
By succinic acid that mol ratio is 1:1.2～1.4 and butanediol, account for the titanium-silicon molecular sieve catalyst of butanediol molal weight 0.1%,
Together add in four-hole boiling flask, 150～180 DEG C of esterifications through the modified alkali magnesium sulfate crystal whisker crossed of silane coupler (KH560)
3h, is warming up to 220 DEG C of polycondensation 5h again after terminating.
After polycondensation reaction terminates, immediately the product in flask is poured in the rectangular disk obtained with made with aluminum foil in advance, be cooled to room temperature, system
Obtain PBS/ alkali magnesium sulfate crystal whisker composite.
Embodiment 1
It is 1g:25ml according to the mass volume ratio of whisker Yu distilled water, takes a certain amount of distilled water in conical flask, regulate with acetic acid
Its pH is 4～5, the silane coupler (KH560) of the 5% of addition whisker quality, stirs in room temperature heat-collecting magnetic stirring device magnetic force
After mixing hydrolysis 120min, add a certain amount of whisker, then after 25 DEG C of magnetic agitation modification 90min, sucking filtration, 80 DEG C of drying
Load sealing bag standby.
By succinic acid and the butanediol of 1.2mol of 1mol, account for the titanium-silicon molecular sieve catalyst of butanediol molal weight 0.1%, change
Property the alkali magnesium sulfate crystal whisker 5g that crosses together add in four-hole boiling flask, be esterified 3h at 150～180 DEG C, after terminating, be warming up to 220 DEG C again
Polycondensation 5h, prepares PBS/ alkali magnesium sulfate crystal whisker composite.
Embodiment 2
The modifying process of alkali magnesium sulfate crystal whisker is with embodiment 1.
By succinic acid and the butanediol of 1.2mol of 1mol, account for the titanium-silicon molecular sieve catalyst of butanediol molal weight 0.1%, change
Property the alkali magnesium sulfate crystal whisker 10g that crosses together add in four-hole boiling flask, be esterified 3h at 150～180 DEG C, after terminating, be warming up to 220 DEG C again
Polycondensation 5h, prepares PBS/ alkali magnesium sulfate crystal whisker composite.
Embodiment 3
The modifying process of alkali magnesium sulfate crystal whisker is with embodiment 1.
By succinic acid and the butanediol of 1.2mol of 1mol, account for the titanium-silicon molecular sieve catalyst of butanediol molal weight 0.1%, change
Property the alkali magnesium sulfate crystal whisker 15g that crosses together add in four-hole boiling flask, be esterified 3h at 150～180 DEG C, after terminating, be warming up to 220 DEG C again
Polycondensation 5h, prepares PBS/ alkali magnesium sulfate crystal whisker composite.
Embodiment 4
The modifying process of alkali magnesium sulfate crystal whisker is with embodiment 1.
By succinic acid and the butanediol of 1.4mol of 1mol, account for the titanium-silicon molecular sieve catalyst of butanediol molal weight 0.1%, change
Property the alkali magnesium sulfate crystal whisker 15g that crosses together add in four-hole boiling flask, be esterified 3h at 150～180 DEG C, after terminating, be warming up to 220 DEG C again
Polycondensation 5h, prepares PBS/ alkali magnesium sulfate crystal whisker composite.
Embodiment 5
The modifying process of alkali magnesium sulfate crystal whisker is with embodiment 1.
By succinic acid and the butanediol of 1.3mol of 1mol, account for the titanium-silicon molecular sieve catalyst of butanediol molal weight 0.1%, change
Property the alkali magnesium sulfate crystal whisker 10g that crosses together add in four-hole boiling flask, be esterified 3h at 150～180 DEG C, after terminating, be warming up to 220 DEG C again
Polycondensation 5h, prepares PBS/ alkali magnesium sulfate crystal whisker composite.
Comparative example 1
Without alkali magnesium sulfate crystal whisker.
By succinic acid and the butanediol of 1.2mol of 1mol, account for the titanium-silicon molecular sieve catalyst of butanediol molal weight 0.1% together
Add in four-hole boiling flask, be esterified 3h at 150～180 DEG C, after terminating, be warming up to 220 DEG C of polycondensation 5h again, prepare PBS/ alkali formula sulphuric acid
Magnesium metal whisker composite.
Comparative example 2
Alkali magnesium sulfate crystal whisker is not modified.
By succinic acid and the butanediol of 1.2mol of 1mol, account for the titanium-silicon molecular sieve catalyst of butanediol molal weight 0.1%, not
Modified alkali magnesium sulfate crystal whisker 5g together adds in four-hole boiling flask, is esterified 3h at 150～180 DEG C, is warming up to 220 DEG C after terminating again
Polycondensation 5h, prepares PBS/ alkali magnesium sulfate crystal whisker composite.
Comparative example 3
By the esterification prepared by this experimental technique, polycondensation product and pass through twin screw through the alkali magnesium sulfate crystal whisker 5g that KH560 is modified
Extruder melt blending, extruding pelletization, it is dried, injection mo(u)lding, prepares PBS/ alkali magnesium sulfate crystal whisker composite.
Detailed data is shown in Table one
Contrasted by embodiment and comparative example, add the PBS through silane coupler modified alkali magnesium sulfate crystal whisker synthesis multiple
The hot strength of condensation material and bending strength are substantially better than pure PBS and add the PBS of unmodified whisker.Simultaneously also superior to molten
Melt the PBS composite that blending extrusion method prepares.
Fig. 3 a, Fig. 3 b the most unmodified (a) and the PBS/ alkali magnesium sulfate crystal whisker composite median surface adhesion condition of modified (b).
As seen from the figure, silane coupler can be obviously improved the interface compatibility of alkali magnesium sulfate crystal whisker and PBS matrix material.
Fig. 2 is the TGA curve after adding whisker, and due to visible, along with the increase of whisker loading, its heat decomposition temperature is obvious
Improve.
The hot strength of the composite prepared by the present invention is substantially better than pure PBS, and this PBS/ alkali magnesium sulfate crystal whisker is multiple
Condensation material have not been reported.
Although the detailed description of the invention of the present invention is described by the above-mentioned accompanying drawing that combines, but not limit to scope
System, one of ordinary skill in the art should be understood that on the basis of technical scheme, and those skilled in the art need not pay
Go out various amendments or deformation that creative work can make still within protection scope of the present invention.
Claims (10)
1. a PBS/ alkali magnesium sulfate crystal whisker composite, it is characterised in that with epoxidised alkali magnesium sulfate crystal whisker, fourth two
Acid and butanediol are raw material, and under catalyst existence condition, in-situ polycondensation forms.
2. composite as claimed in claim 1, it is characterised in that the hot strength of described composite is 36.5～46.3Mpa；
Bending strength is 29.4～44.1Mpa.
3. composite as claimed in claim 1, it is characterised in that described epoxidised alkali magnesium sulfate crystal whisker, succinic acid and
The mass ratio of butanediol is 5～15:118:108～126.
4. composite as claimed in claim 1, it is characterised in that described epoxidised alkali magnesium sulfate crystal whisker is by alkali formula sulphuric acid
Magnesium whisker obtains through silane coupler KH560 modification.
5. the preparation method of a PBS/ alkali magnesium sulfate crystal whisker composite, it is characterised in that including:
The surface of alkali magnesium sulfate crystal whisker is carried out epoxide modified, obtains epoxidised alkali magnesium sulfate crystal whisker；
With epoxidised alkali magnesium sulfate crystal whisker, succinic acid and butanediol as raw material, carry out contracting in situ under catalyst existence condition
Poly-, to obtain final product.
6. method as claimed in claim 5, it is characterised in that described epoxide modified modifying agent is silane coupler KH560.
7. method as claimed in claim 5, it is characterised in that described epoxidised alkali magnesium sulfate crystal whisker, succinic acid and fourth two
The mass ratio of alcohol is 5～15:118:108～126.
8. method as claimed in claim 6, it is characterised in that the consumption of described silane coupler KH560 is alkali magnesium sulfate
The 3～7% of whisker quality.
9. the PBS/ alkali magnesium sulfate crystal whisker composite that prepared by the method described in any one of claim 5-8.
10. the PBS/ alkali magnesium sulfate crystal whisker composite described in claim 1-4,9 any one is preparing degradation plastic, rubber
Application in glue or its additive.
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| CN108276605A (en) * | 2018-01-26 | 2018-07-13 | 青岛科技大学 | A method of preparing inorganic crystal whisker/POSS hybrid materials using sulfydryl-alkene click-reaction |
| CN109880312A (en) * | 2019-01-29 | 2019-06-14 | 安徽天光传感器有限公司 | A kind of preparation method of sensor outer housing modified butanediol ester poly succinic acid composite material |
| CN112547014A (en) * | 2020-12-07 | 2021-03-26 | 神美科技有限公司 | Preparation method of carbon-doped magnesium hydroxide whisker-loaded rare earth metal defluorination material |
| JPWO2021199840A1 (en) * | 2020-03-30 | 2021-10-07 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107254147A (en) * | 2017-06-09 | 2017-10-17 | 陕西科技大学 | A kind of preparation method of degradable wood plastic composite |
| CN108276605A (en) * | 2018-01-26 | 2018-07-13 | 青岛科技大学 | A method of preparing inorganic crystal whisker/POSS hybrid materials using sulfydryl-alkene click-reaction |
| CN108276605B (en) * | 2018-01-26 | 2020-02-18 | 青岛科技大学 | Method for preparing inorganic whisker/POSS hybrid material by utilizing sulfydryl-alkene click reaction |
| CN109880312A (en) * | 2019-01-29 | 2019-06-14 | 安徽天光传感器有限公司 | A kind of preparation method of sensor outer housing modified butanediol ester poly succinic acid composite material |
| CN109880312B (en) * | 2019-01-29 | 2021-10-29 | 五河县宜然知识产权服务有限公司 | Preparation method of modified poly (butylene succinate) composite material for sensor shell |
| JPWO2021199840A1 (en) * | 2020-03-30 | 2021-10-07 | ||
| CN112547014A (en) * | 2020-12-07 | 2021-03-26 | 神美科技有限公司 | Preparation method of carbon-doped magnesium hydroxide whisker-loaded rare earth metal defluorination material |
| CN112547014B (en) * | 2020-12-07 | 2022-06-28 | 神美科技有限公司 | Preparation method of carbon-doped magnesium hydroxide whisker-loaded rare earth metal defluorination material |
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| CN106008931B (en) | 2017-09-19 |
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