CN101200575A - Montmorillonite modified polyester and preparation method thereof - Google Patents
Montmorillonite modified polyester and preparation method thereof Download PDFInfo
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- CN101200575A CN101200575A CNA2006101473807A CN200610147380A CN101200575A CN 101200575 A CN101200575 A CN 101200575A CN A2006101473807 A CNA2006101473807 A CN A2006101473807A CN 200610147380 A CN200610147380 A CN 200610147380A CN 101200575 A CN101200575 A CN 101200575A
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Abstract
The present invention provides a preparation method of imvite modified polyester, including the following steps: (a) aqueous mixture of 1 to 4wtg. imvite original soil, 50 to 80wtg. glycol and 50 to 500wtg. water is provided; (b) the aqueous mixture in step (a) is mixed with 40 to 50wtg. terephthalic acid dimethyl ester; (c) the mixture in step (b) is polymerized under the temperature of 160 to 290 DEG C so as to obtain the imvite modified polyester. The present invention also provides composite material prepared by the method. The polyester composite material has excellent air barrier property and crystallization property.
Description
Technical field
The present invention relates to a kind of crystal property height, polynite/PET nano composite material and in-situ preparation method thereof that barrier properties for gases is good.
Background technology
PET is a kind of polymkeric substance of high comprehensive performance, is widely used in fiber, film and engineering plastics.But because its heat-drawn wire is low, crystallization rate is also low, with and poor dimensional stability, shortcoming such as barrier properties for gases is also bad has limited its widespread use in the engineering plastics field.
Particularly from early 1980s, PET progressively becomes the fastest-rising resin of consumption in world's packaging industry.But PET is general to the barrier of oxygen, carbonic acid gas and some organic solvents, does not satisfy requirement far away for some extra package things; The PET crystallization rate is lower in the process of processing simultaneously, has increased the cycle of machine-shaping, and this has just limited the application of PET in wrapping material.In order to make full use of the advantage of PET, can solve the problem of crystallinity and barrier difference again, many people are devoted to improve the research of PET modification, particularly pass through the filling-modified of mineral ion.
The method of the industrial mineral filler that adds in PET is a melt blending, the mineral filler of inserting has: glass fibre, talcum powder, kaolin, wollastonite etc., these methods can be improved PET crystallinity and barrier properties for gases to a certain extent, but because the melt blended compound energy consumption of PET is very high, be easy to degraded, equipment attrition is big, and the result is satisfied not to the utmost.Also there is research to report and utilizes organic nucleocapsid structure modified PET, though the PET matrix material that obtains has mechanical property preferably,, the processing mold temperature of matrix material is higher, and heat-drawn wire (HDT) reduces significantly.Also have report to prepare the PET matrix material with fluorine mica, preparation technology's more complicated, cost is higher.
In sum, this area lacks a kind of polyester composite that obtains desired gas barrier and crystal property and preparation method thereof.
Summary of the invention
One object of the present invention is to obtain the preparation method of the polyester composite of excellent gas barrier and crystal property.
Another object of the present invention is to obtain a kind of polyester composite with excellent gas barrier and crystal property.
A further object of the present invention is to provide the purposes of montmorillonite modified polyester of the present invention.
Provide a kind of preparation method of montmorillonite modified polyester in a first aspect of the present invention, it comprises the steps: that (a) provides the aqueous mixture of ethylene glycol in 50～500 weight parts waters of 1～4 weight part original montmorillonoid soil, 50～80 weight parts; (b) aqueous mixture that step (a) is obtained and the dimethyl terephthalate (DMT) of 40～80 weight parts obtain mixture; (c) step (b) gained mixture carries out polymerization under 160～290 ℃, obtains described montmorillonite modified polyester.
In a preferred embodiment of the present invention, the aqueous mixture of step (a) obtains as follows: the aqueous dispersion of 1～4 weight part original montmorillonoid soil in 50～500 weight parts waters is provided, the ethylene glycol that described dispersion adds 50～80 weight parts mixes, and the gained mixture is removed moisture content and obtained described aqueous mixture.
In a preferred embodiment of the present invention, the expanding material that also adds 0.1～0.5 weight part in the aqueous dispersion of described step (a).
Preferably described expanding material is the polyoxyethylene glycol of molecular weight between 500～10000.
Preferably described component is 0.25 ± 0.05 weight part,
In a preferred embodiment of the present invention, the esterifying catalyst that also adds 0.05～0.15 weight part in the mixture of described step (b).
Preferably, described esterifying catalyst is the antimonous oxide of 0.01～0.03 weight part, the lime acetate of 0.04～0.12 weight part.
In a preferred embodiment of the present invention, the polyreaction in the described step (c) comprises transesterify stage and polymerization stage, and the described transesterify stage carries out under 160～220 ℃; Described polymerization stage is not higher than under the 60Pa at 270～290 ℃, vacuum tightness and carries out.
In a preferred embodiment of the present invention, comprise the steps:
(i) original montmorillonoid soil with 1～4 weight part was stirring 1～5 hour in 80～100 ℃ of water of its 50～500 times of parts by weight, added 0.1～0.5 polyoxyethylene glycol then and disperseed 1～5 hour, obtained the aqueous dispersion of described polynite and polyoxyethylene glycol;
(ii) the dispersion that obtains in step (i) is mixed with the ethylene glycol of described component, obtains aqueous mixture;
The aqueous mixture that (iii) described step (ii) obtains is removed moisture, obtains the mixture of described step (a).
Preferably, be separated into ultra-sonic dispersion in the described step (i).Preferably, between ultrasonic power 40～80W.
Preferably, the water in the described step (i) is ebullient water.
Preferably, the stirring intensity in the described step (i) is 100～300r/min.
The montmorillonite modified polyester that another aspect of the present invention provides a kind of method of the present invention to make, the molecular weight 20000～25000 of described polyester, wherein polynite accounts for 1～4 weight % of described polyester, and described polynite is scattered in the described polyester with the disperse phase of the size of 10～100nm.
In a preferred embodiment of the present invention, described disperse phase is a lamella, the thickness 1.5～2.0nm of described lamella.
In a preferred embodiment of the present invention, the specific surface area of the internal surface of described lamella is 200-800m
2/ g.
In a preferred embodiment of the present invention, 210～220 ℃ of the Tcs of described polyester, oxygen transmission coefficient 4.01～2.15 * 10
-3Cm
3Mm/m
2D 0.1MPa.
Another aspect of the present invention is to provide a kind of purposes of montmorillonite modified polyester of the present invention, is applied to the engineering plastics field and uses as wrapping material.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of original soil and each product.
X-coordinate is an angle of diffraction among the figure, and ordinate zou is a diffracted intensity.
Embodiment
The inventor is through extensive and deep research, by improving preparation technology, utilize water to carry out in-situ polymerization as dispersion agent and obtain a kind of polyester/Nanometer Composite Material Of Montmorillonite And Its Preparation Method, the barrier properties for gases and the crystal property of the prepared polyester/Nano composite material of montmorillonite of the present invention all improve a lot.
The implication of " original montmorillonoid soil " of the present invention is the polynite that does not have through the processing that organises.
" lamellar spacing " of matrix material of the present invention be MMT sheet interlayer spacing from.
Below preparation method of the present invention is described in detail:
The preparation method
The preparation method of montmorillonite modified polyester of the present invention comprises the steps:
(a) provide the aqueous mixture of ethylene glycol in 50～500 weight parts waters of 1～4 weight part original montmorillonoid soil, 50～80 weight parts;
(b) aqueous mixture that step (a) is obtained mixes with the dimethyl terephthalate (DMT) of 40～80 weight parts, obtains mixture;
(c) step (b) gained mixture carries out polymerization under 160～290 ℃, obtains described montmorillonite modified polyester.
In order to make dispersion more even, preferably, the aqueous mixture of step (a) obtains as follows: the aqueous dispersion of 1～4 weight part original montmorillonoid soil in 50～500 weight parts waters is provided, the ethylene glycol that described dispersion adds 50～80 weight parts mixes, and the gained mixture is removed moisture content and obtained described aqueous mixture.
In order to improve the dispersiveness of polynite, can also add the expanding material of 0.1～1 weight part in the described aqueous dispersion, preferred 0.1～0.5 weight part.Described expanding material is a polyethers, for example specifically is to be selected from polyoxyethylene glycol, polytetrahydrofuran, poly(propylene oxide) etc.Polyoxyethylene glycol preferably, described solubilizing agent is the polyoxyethylene glycol of molecular weight between 500～10000.
For fast reaction speed, can also add the esterifying catalyst of 0.05～0.15 weight part in the mixture of described step (b).Described esterifying catalyst is not particularly limited, only otherwise purpose of the present invention is produced restriction to get final product.For example specifically be lime acetate, zinc acetate, cobaltous acetate, antimonous oxide etc.Be preferably the mixed catalyst that lime acetate and antimonous oxide are formed, antimonous oxide 0.01～0.03 weight part; Lime acetate 0.04～0.12 weight part.
Polyreaction in the described step (c) comprises transesterify stage and polymerization stage,
The described transesterify stage carries out under 160～220 ℃;
Described polymerization stage is not higher than under the 60Pa at 270～290 ℃, vacuum tightness and carries out.
In the transesterify stage, synthesize diethyl terephthalate by dimethyl terephthalate (DMT).
In a preferred embodiment of the present invention, comprise the steps:
(i) original montmorillonoid soil with described component was stirring 1～5 hour in 80～100 ℃ of water of its 50～500 times of parts by weight, added described component polyoxyethylene glycol then and disperseed 1～5 hour, obtained the aqueous dispersion of described polynite and polyoxyethylene glycol;
(ii) the dispersion that obtains in step (i) is mixed with the ethylene glycol of described component, obtains aqueous mixture;
The aqueous mixture that (iii) described step (ii) obtains is removed moisture, obtains the mixture of described step (a).
Preferably, be separated into ultra-sonic dispersion in the described step (i).Preferably, ultrasonic power is between 40～80w.
Preferably, the water in the described step (i) is ebullient water.
Preferably, the stirring intensity in the described step (i) is 100～300r/min.
Feedstock detail of the present invention is as follows:
Polynite
The polynite raw material that the present invention was suitable for is an original soil, and its molecular formula is: (OH)
4Si
8Al
4O
20
The original soil that the present invention adopts for example is that the unit cell of polynite is made up of two-layer silicon-oxy tetrahedron therebetween layer of aluminum oxygen octahedra, connects by public Sauerstoffatom between the two particularly.More specifically, montmorillonite layer thickness is about 1.2nm, and the internal surface of lamella has negative charge, its specific surface area 200-800m
2/ g, interlayer cation are Na
+Deng exchangeable cation.
Transesterify
The polyester/clay nano composite material of present method adopts the method for transesterify synthetic.Raw material adopts dimethyl terephthalate (DMT) (DMT), ethylene glycol (EG), antimonous oxide, lime acetate, polynite (MMT) and polyoxyethylene glycol (PEG).Wherein the used PEG molecular weight of the present invention is 1000.
The method for preparing nano composite material is as follows:
Original montmorillonoid soil is scattered in 50～500 times of ebullient deionized waters with its quality, and violent stirring 1～5 hour added the PEG ultra-sonic dispersion 3 hours then, added then after a certain amount of EG mixes, and removed moisture.Mixture after dewatering is added reaction wherein, in reactor, add properly mixed DMT, EG, antimonous oxide and lime acetate again, under nitrogen protection, be warmed up to 160～220 ℃ of reactions 3 hours; Keep vacuum tightness and be lower than 60Pa, be warmed up to 270～290 ℃ of reactions 1～3 hour, stopped reaction takes out product.In the gained matrix material in the size dispersion and PET of disperse phase with 10～100nm.
Details are as follows for montmorillonite modified polyester of the present invention:
Montmorillonite modified polyester
The montmorillonite modified polyester that method of the present invention makes, the molecular weight 20000～25000 of described polyester, weight-average molecular weight, wherein polynite accounts for 1～4 weight % of described polyester, and described polynite is scattered in the described polyester with the disperse phase of the size of 10～100nm.
Preferably, described disperse phase is a lamella, about the thickness 1.5～2.0nm of described lamella.More preferably be the specific surface area 200-800m of described lamella internal surface
2/ g.
210～220 ℃ of the Tcs of polyester of the present invention, oxygen transmission coefficient 4.01～2.15 * 10
-3Cm
3Mm/m
2D 0.1MPa.
The invention has the advantages that:
Adopt the PET nano composite material of the inventive method preparation, its polynite disperse phase has very large interfacial area with 10～100nm size dispersion, can give full play to rigidity, thermotolerance and the barrier properties for gases of polynite.The PET/MMT matrix material that adopts the present invention's preparation has higher molecular weight and molecular weight distribution is narrower.
Below in conjunction with specific embodiment, further illustrate the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, for example is " condition in the smooth organic chemistry handbook of Bel Si (Chemical Industry Press, 1996), or the condition of advising according to manufacturer.Ratio and per-cent are based on weight, unless stated otherwise.
Embodiment 1:
1 part of polynite is scattered in 100 parts of ebullient water, stirred 2 hours, add 0.2 part of molecular weight again and be 1000 PEG, ultra-sonic dispersion adds 80 parts EG after 3 hours, goes out wherein moisture after the dispersion, adds in the reactor then; The DMT, 0.03 part antimonous oxide and 0.12 part the lime acetate that in reactor, add 80 parts again.Be warmed up to 180 ℃ of reactions 2 hours under the nitrogen protection, keep vacuum tightness and be lower than 60Pa, be warmed up to 280 ℃ of reactions 3 hours, stopped reaction takes out product.
Embodiment 2:
With embodiment 1, the content that only changes MMT is 2 parts.
Embodiment 3:
With embodiment 1, the content that only changes MMT is 3 parts.
Embodiment 4:
With embodiment 1, the content that only changes MMT is 4 parts.
Each embodiment product and original soil carry out the small angle X-ray diffraction test: use Rigaku D/Max-III type X-ray diffractometer, test condition is the Cu target, and scanning angle is 0～100, and it the results are shown in Figure 1.
Last figure curve corresponds respectively to 1,2,3 and 4 of embodiment from top to bottom among Fig. 1; Figure below is the X-ray diffraction curve of original soil.By the Bragg formula:
2dsinθ＝nλ
And the pairing diffraction angle of diffraction peak is calculated and can be got in the spectrogram, the MMT sheet interlayer spacing is from being 1.81nm in the PET matrix, the interlamellar spacing of original soil then is 1.25nm, in the prepared PET/MMT nano composite material of the present invention that hence one can see that, the laminated structure of MMT obtains very big change, it exists to peel off with intercalation configuration in the PET matrix, and dispersion size is a nano level.
The dsc analysis of product among each embodiment: the PET/MMT matrix material of thorough drying is carried out dsc analysis, use instrument to be NETZSCH DSC 200, intensification and cooling rate are 10 ℃/min, be warmed up to 280 ℃ by 0 ℃, keep 5min, and then be cooled to 0 ℃, be warmed up to 280 ℃ again.Record its Tc and see attached list 1.
The permeability analysis of product among each embodiment: the PET/MMT matrix material is made required sample by GB1038-70, the oxygen transmission coefficient of test sample on Mocon-100 type gas permeabillty tester.Measurement result sees attached list 1.
Subordinate list 1:
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. the preparation method of a montmorillonite modified polyester is characterized in that, comprises the steps:
(a) provide the aqueous mixture of ethylene glycol in 50～500 weight parts waters of 1～4 weight part original montmorillonoid soil, 50～80 weight parts;
(b) aqueous mixture that step (a) is obtained and the dimethyl terephthalate (DMT) of 40～80 weight parts obtain mixture;
(c) step (b) gained mixture carries out polymerization under 160～290 ℃, obtains described montmorillonite modified polyester.
2. the method for claim 1 is characterized in that,
The aqueous mixture of step (a) obtains as follows: the aqueous dispersion of 1～4 weight part original montmorillonoid soil in 50～500 weight parts waters is provided, the ethylene glycol that described dispersion adds 50～80 weight parts mixes, and the gained mixture is removed moisture content and obtained described aqueous mixture.
3. method as claimed in claim 2 is characterized in that, also adds the expanding material of 0.1～0.5 weight part in the aqueous dispersion of described step (a).
4. the method for claim 1 is characterized in that, also adds the esterifying catalyst of 0.05～0.1 weight part in the mixture of described step (b).
5. the method for claim 1 is characterized in that, the polyreaction in the described step (c) comprises transesterify stage and polymerization stage,
The described transesterify stage carries out under 160～220 ℃;
Described polymerization stage is not higher than under the 60Pa at 270～290 ℃, vacuum tightness and carries out.
6. a montmorillonite modified polyester that makes as the described method of claim 1～5 is characterized in that,
The molecular weight 20000～25000 of described polyester;
Wherein polynite accounts for 1～4 weight % of described polyester, and described polynite is scattered in the described polyester with the disperse phase of the size of 10～100nm.
7. polyester as claimed in claim 6 is characterized in that, described disperse phase is a lamella, the thickness 1.5～2.0nm of described lamella.
8. polyester as claimed in claim 7 is characterized in that, the specific surface area of the internal surface of described lamella is 200-800m
2/ g.
9. polyester as claimed in claim 6 is characterized in that, 210～220 ℃ of the Tcs of described polyester, oxygen transmission coefficient 4.01～2.15 * 10
-3Cm
3Mm/m
2D 0.1MPa.
10. the purposes of a montmorillonite modified polyester as claimed in claim 1 is characterized in that being applied to the engineering plastics field and uses as wrapping material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101473807A CN101200575A (en) | 2006-12-15 | 2006-12-15 | Montmorillonite modified polyester and preparation method thereof |
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|---|---|---|---|
| CNA2006101473807A CN101200575A (en) | 2006-12-15 | 2006-12-15 | Montmorillonite modified polyester and preparation method thereof |
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| CN101200575A true CN101200575A (en) | 2008-06-18 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409916A (en) * | 2018-04-18 | 2018-08-17 | 西北师范大学 | A kind of preparation method of LSOH anti-flaming unsaturated polyester resin composite material |
| CN109135401A (en) * | 2018-07-05 | 2019-01-04 | 安徽博泰氟材料科技有限公司 | A kind of F-C paint protection filler and preparation method thereof |
-
2006
- 2006-12-15 CN CNA2006101473807A patent/CN101200575A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409916A (en) * | 2018-04-18 | 2018-08-17 | 西北师范大学 | A kind of preparation method of LSOH anti-flaming unsaturated polyester resin composite material |
| CN108409916B (en) * | 2018-04-18 | 2020-08-21 | 西北师范大学 | Preparation method of halogen-free low-smoke flame-retardant unsaturated polyester resin composite material |
| CN109135401A (en) * | 2018-07-05 | 2019-01-04 | 安徽博泰氟材料科技有限公司 | A kind of F-C paint protection filler and preparation method thereof |
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Open date: 20080618 |