CN105385120B - A kind of preparation method of PET organic intercalations α ZrP composites - Google Patents
A kind of preparation method of PET organic intercalations α ZrP composites Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of PET organic intercalations α ZrP composites, comprises the following steps：1) the organic intercalation α ZrP that will be obtained with silane coupler and α ZrP intercalations and fully dry PET are by 20:80~80:20 weight obtains mixed material than mixing, and this mixed material is made the PET master batch of the ZrP of α containing organic intercalation；2) by step 1) PET master batch of the obtained ZrP of α containing organic intercalation and PET it is well mixed so that the mass percent of organic intercalation α ZrP is 1~10% in mixture, then uses injection machine injection moulding, obtains product.α ZrP and the PET blending of silane coupler orgnic-intercalation modification are first made the present invention PET master batch of the ZrP of α containing organic intercalation, then pure PET is mixed into by a certain percentage is molded into product, a kind of new technology for being suitable for rule film production greatly is thus provided, the PET products to water and gas excellent in barrier property can be obtained.
Description
Technical field
The present invention relates to organic intercalation α-ZrP technical field of composite materials, more particularly to a kind of PET- organic intercalations α-
The preparation method of ZrP composites.
Background technology
Polyethylene terephthalate (PET) is a kind of semi-crystalline polymer, with good chemical resistance, thermally-stabilised
Property, high intensity and spinnability, have a wide range of applications in fields such as fiber, film and engineering plastics.At present, high barrier, height
Heat endurance and the good material current demand of the transparency are very big, with PET as matrix, are entered by physically or chemically modified method
Row is modified, with feasible route is facilitated, the product that PET is matrix is had water proof, the choke function for meeting and requiring, as compound
One of focus of investigation of materials and application.Although PET is convenient better than common plasticses in ventilative, water penetration, vacuum can only
Maintain 9~12 months, water tariff collection 3~6 months, can not meet vacuum test tube vacuum, moisture content and kept for 1.5~2 years effectively
The demand of phase, also can not meet requirement of the beverage bottle to gas hyposmosis, have a strong impact on promoting the use of for product.
In the prior art, the study on the modification for PET is broadly divided into blending and modifying and face coat is modified, and blending and modifying is
PET is mixed with water repellent, the preferable PEN of gas barrier properties or the material such as glass fibre, PS, PE, PP, its water repellent and gas barrier property is improved
Can, but there are problems that product cost is high, product is lacked competitiveness or effect can not reach；Face coat is modified
It is that polyphenylene oxides ester and its modifier series of products are coated in pet sheet face, gas, extension moisture and vacuum is intercepted so as to play
The effect of retention time, but this means technological requirement is high, it is difficult to mass produce.
It is expected to improve barrier properties of the PET as container containing by being combined with basic zirconium phosphate layered phosphates.Polymer/layer
Shape phosphate (α type basic zirconium phosphates, abbreviation α-ZrP) nano composite material has more advantages, extends existing macromolecular material
Range of application, be with a wide range of applications and prospect.Except can be widely used for the aspects such as film, packaging, fiber, these are answered
Condensation material can be used for engineering plastics, the container material higher to material performance requirement (such as：Beer bottle, heparin tube etc.).
In the prior art, the method for preparing PET/ α-ZrP nano composite materials is probably divided into two major classes, i.e.,：It is in-situ inserted
Composite algorithm and polymer melt graft process.PET/ α-ZrP the nano composite materials for using at present are mostly with the work of in-situ polymerization
What skill was manufactured, what is obtained is exfoliated α-ZrP laminar composites, but, situ aggregation method prepares PET/ α-ZrP and receives
The process route of nano composite material is more complicated, and economic benefit is not high, and the technology for developing melt directly graft process has urgent at present
Demand.Wherein, melting intercalation method is applied to and is carried out on existing contour machining equipment, greatly improves economic benefit, but
It is in the hydroxyl that the surface of α-ZrP and interlayer have existed big, to show very strong hydrophily, causes α-ZrP in polymer melt
Dispersion is more uneven, and the intercalation and stripping for causing α-ZrP lamellas are difficult to fully achieve.
The content of the invention
It is an object of the present invention to being directed to, existing PET barriers can not meet heparin tube, the use requirement of liquid beverage is asked
A kind of topic, there is provided preparation method of PET- organic intercalations α-ZrP composites, can be obtained to water to vapour lock with easy technique
The good PET products of separating performance.
In order to solve the above problems, the present invention is adopted the following technical scheme that：
A kind of preparation method of PET- organic intercalations α-ZrP composites of the invention, comprises the following steps：
1) α-ZrP are scattered in the mixed solution of water and ethanol；
2) small molecule amine reaction is added；
3) silane coupler is added dropwise again to continue to react；
4) solid product separating, washing and drying can obtain modified α-ZrP；
5) the modified α-ZrP are processed under the conditions of 250~320 DEG C, that is, obtain organically-modified α-ZrP；
6) the organically-modified α-ZrP and abundant dry PET are pressed 20:80~80:20 weight is mixed than mixing
Compound material, this mixed material is made the PET master batch of-ZrP of α containing organic intercalation；
7) by step 6) PET master batch of the obtained-ZrP of α containing organic intercalation and PET be well mixed so that have in mixture
The mass percent of machine transplanting of rice layer α-ZrP is 1~10%, then uses injection machine injection moulding, obtain the PET- organic intercalations α-
ZrP composites, the light transmittance of the PET- organic intercalation α-ZrP composites, more than 65~82%, is pure PET in visible region
77~97%, OTR oxygen transmission rate reduction about 20~40%；Permeability rate reduction by 35~65%.
As preferred technical scheme：
The preparation method of PET- organic intercalations α-ZrP composites of the present invention, step 1) in, the water and ethanol
Mixed solution, the mass ratio of water and ethanol is 1:2~1:8；The concentration of α-ZrP is 0.005~0.02g/ml after dispersion；It is described
Dispersion refers to ultrasonic and mechanical agitation at ambient temperature；Churned mechanically rotating speed be 200~800r/min, the time be 20~
50min；The ultrasound refers to that at ambient temperature, ultrasonic power is 50~90W, and the time is 20~50min.
The preparation method of PET- organic intercalations α-ZrP composites of the present invention, small molecule amine and α-ZrP mole
Than being 1:2.0~1:4.0, the time for adding small molecule amine reaction is 0.6~1.8h；The small molecule amine be methylamine, ethamine or
N-propylamine.
The preparation method of PET- organic intercalations α-ZrP composites of the present invention, the dripping quantity of silane coupler with
The mass ratio of α-ZrP is 0.5:1~2.0:1；Drop rate is 0.1~1.5ml/min；The time for continuing to react for 3~
8h；The silane coupler is 3- aminopropyls-triethoxysilane (APTES), 3- aminopropyls-trimethoxy silane
Or γ-methyl-acryloyloxy-propyl-trimethoxysilane (MPMS) etc. (APTMS).
The preparation method of PET- organic intercalations α-ZrP composites of the present invention, step 4) in, solid product with it is molten
Agent is separated and uses Rotary Evaporators；The washing be first acetone that concentration is 90~98% and water mixed solution immersion 24~
36h, cleans 3~5 times up to the reaction raw materials of noresidue in product with a large amount of acetone solns afterwards；The drying is dried to be placed in vacuum
In case, 60~80 DEG C, 24~36h is dried under the conditions of 0.05~0.1MPa of vacuum；Step 5) in, the treatment refers to will be modified
α-ZrP 3~10min is bakeed under the conditions of 250~320 DEG C.
The preparation method of PET- organic intercalations α-ZrP composites of the present invention, the organically-modified α-ZrP outward appearances
It is white powder；Organically-modified α-the ZrP are lamellar compound, and interlamellar spacing is 1.60~1.90nm；The organically-modified α-
ZrP is made up of α-ZrP and silane coupler, and silane coupler is inserted in α-ZrP interlayers, grafting of the silane coupler on α-ZrP
Rate is 6~18%；Organically-modified α-ZrP the initial decomposition temperatures are 340~400 DEG C；Organically-modified α-the ZrP can be equal
It is even to be dispersed in non-polar organic solvent n-hexane.
The preparation method of PET- organic intercalations α-ZrP composites of the present invention, step 6) in, the abundant drying
PET be at a temperature of 120~180 DEG C dry 4~8h：By the mixed material of abundant dry PET and organic intercalation α-ZrP
First mixed with banbury, then melt blending, granulation at a temperature of 245~300 DEG C with double screw extruder, obtain containing the machine transplanting of rice
The PET master batch of layer α-ZrP.
The preparation method of PET- organic intercalations α-ZrP composites of the present invention ,-the ZrP's of α containing organic intercalation
The weight/mass percentage composition of organic intercalation α-ZrP is 20~80% in PET master batch.
The preparation method of PET- organic intercalations α-ZrP composites of the present invention, step 7) in, α containing organic intercalation-
4~8h is first dried at a temperature of 120~180 DEG C after the PET master batch and PET of ZrP are well mixed, then is molded with injection machine.
The preparation method of PET- organic intercalations α-ZrP composites of the present invention, step 7) in, α containing organic intercalation-
The PET master batch of ZrP and the mixture of PET are molded at a temperature of 265~330 DEG C with injection machine；The obtained PET- is organic
The weight/mass percentage composition that organic intercalation α-ZrP account for composite in intercalation α-ZrP composites is 1~10%.
Beneficial effect
Method of modifying from prior art is different, and be total to for the α-ZrP and PET of silane coupler orgnic-intercalation modification by the present invention
It is mixed, the PET master batch of-ZrP of α containing organic intercalation is first made, pure PET is then mixed into by a certain percentage is molded into product, thus provide
A kind of new technology for being suitable for large-scale production, can obtain the PET product good to water and gas barrier.
The present invention manages the injection molding technique of (including heparin tube) product without original PET is changed, using characteristic, obtain
Product can be used for the cosmetics containers such as heparin tube, beer bottle, scent flask, and these are needed in the good container of barrier property.
The present invention during processed finished products can use with existing PET identicals working process parameter, even if at 340 DEG C
Under temperature conditionss, the organic intercalation α-ZrP of silane coupler orgnic-intercalation modification also do not decompose,
And in the prior art, common organic intercalation α-ZrP are just having decomposition higher than 250 DEG C, the processing temperature far below PET
Degree, thus the quality of manufactured goods can be influenceed, the present invention can still be used during processed finished products and process work with existing PET identicals
Skill parameter, technique simplifies.
The present invention is convenient because the organic intercalation α-ZrP preparation technologies that use amplify, efficiency high, and needs in the prior art
The technique of blending additive is compared, and is capable of achieving large-scale production, does not influence production efficiency, advantage of lower cost.
It is of the invention compared with the technique such as in-situ inserted composite algorithm and polymer melt graft process in the prior art, be capable of achieving big
Due to the method using masterbatch filling in large-scale production, and technical process, the problems such as disperseing irregular is overcome.
Brief description of the drawings
Fig. 1 is the process schematic for preparing organically-modified α-ZrP, and wherein α-ZrP are first through n-propylamine (n-propylamine)
, then there is graft reaction in pre- intercalation, eventually pass heat treatment (heat- with 3- aminopropyls-triethoxysilane (APTES)
Treatment organically-modified α-ZrP) are obtained final product.
Fig. 2 is the X-ray diffractogram (ordinate is relative intensity, and abscissa is 2 θ angles) of the organically-modified α-ZrP for preparing,
Wherein α-ZrP-PA-APTES are anti-with 3- aminopropyls-triethoxysilane (APTES) generation grafting after propylamine (PA) is supportted in advance
α-ZrP, the α-ZrP-PA-APTES-HT for answering are by the α-ZrP-PA-APTES after treatment.
Fig. 3 is the thermogravimetric curve (ordinate is quality, and abscissa is temperature) of the organically-modified α-ZrP for preparing, wherein
α-ZrP-PA-APTES are that graft reaction occurs with 3- aminopropyls-triethoxysilane (APTES) after propylamine (PA) is supportted in advance
α-ZrP, α-ZrP-PA-APTES-HT are by the α-ZrP-PA-APTES after treatment.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Fixed scope.
In embodiments of the invention：
The computing formula of interlamellar spacing is：D=λ/2sin θ；λ is the wavelength of X-ray, and θ is incident X-rays and corresponding crystal face
Angle.
The interlamellar spacing of modified used α-ZrP is 0.76nm (2 θ=10.8 °).
The computing formula of grafting rate is as follows：
The quality of the quality of grafting rate (%)=organic component/unmodified α-ZrP.
Embodiment one
A kind of preparation method of PET- organic intercalations α-ZrP composites, as shown in figure 1, to prepare organically-modified α-ZrP
Process schematic, wherein α-ZrP first through n-propylamine (n-propylamine) pre- intercalation, then with the ethoxy of 3- aminopropyls-three
There is graft reaction in base silane (APTES), eventually pass heat treatment (heat-treatment) and obtain final product organically-modified α-ZrP, walk
Suddenly it is：
1) by α-ZrP at ambient temperature, ultrasound and mechanical agitation, ultrasonic power is 50W, and the time is 20min；Machinery is stirred
The rotating speed mixed is 200r/min, and the time is scattered in the mixed solution of water and ethanol for 20min, and water is 1 with the mass ratio of ethanol:
2；The concentration of α-ZrP is 0.005g/ml after dispersion；
2) reaction of small molecule n-propylamine is added, n-propylamine is 1 with the mol ratio of α-ZrP:2.0, add n-propylamine reaction
Time is 0.6h；
3) silane coupler 3- aminopropyls-triethoxysilane (APTES) is added dropwise again to continue to react；The dropwise addition of APTES
Amount is 0.5 with the mass ratio of α-ZrP:1；Drop rate is 0.1ml/min；The time for continuing to react is 3h；
4) solid product separating, washing and drying can obtain modified α-ZrP, and solid product separates use with solvent
Rotary Evaporators；Washing is first to soak 24h with the mixed solution of water in the acetone that concentration is 90%, clear with a large amount of acetone solns afterwards
3 times are washed up to the reaction raw materials of noresidue in product；Dry to be placed in vacuum drying oven, 60 DEG C, under the conditions of vacuum 0.05MPa
Drying 24h；
5) modified α-ZrP bakee 3min under the conditions of 250 DEG C, that is, obtain organically-modified α-ZrP, and the organically-modified α-
ZrP outward appearances are white powder, and are lamellar compound, as shown in Fig. 2 the interlamellar spacing of the organically-modified α-ZrP is 1.74nm (2 θ
=5.06 °)；Organically-modified α-the ZrP are by α-ZrP and silane coupler 3- aminopropyls-triethoxysilane (APTES) group
Into, APTES is inserted in α-ZrP interlayers, as shown in figure 3, grafting rates of the APTES on α-ZrP is 13.78%, the organically-modified α-
The initial decomposition temperature of ZrP is 368 DEG C；Organically-modified α-ZrP can be dispersed in non-polar organic solvent n-hexane；
6) PET is dried into 8h at 120 DEG C, then by 3- aminopropyls-triethoxysilane (APTES) intercalation α-ZrP with
PET is according to 20:80 (W/W) double screw extruders melt blending, granulation at a temperature of 245 DEG C, obtain amino containing 20%3-
The PET master batch material of propyl-triethoxysilane (APTES) intercalation α-ZrP；
7) it is 1% by the weight/mass percentage composition of α-ZrP in end article is set, the above-mentioned ethoxy of 3- aminopropyls-three will be contained
The PET master batch of base silane (APTES) intercalation α-ZrP is well mixed with PET, then dries 5h at 130 DEG C, is used at 265 DEG C
Injection obtains the modified PET pieces of organic α-ZrP on injection machine.
Through inspection, the final α-ZrP contents of the plastic sheet that the present embodiment is obtained are 1.19%, and light transmittance is super in visible region
70% is crossed, is the 83% of pure PET；Final OTR oxygen transmission rate reduction about 26%；Permeability rate reduction by 40%.The technique can be used to prepare
The heparin tube of good barrier property.
Embodiment two
A kind of preparation method of PET- organic intercalations α-ZrP composites, comprises the following steps：
1) by α-ZrP at ambient temperature, ultrasound and mechanical agitation, ultrasonic power is 90W, and the time is 50min；Machinery is stirred
The rotating speed mixed is 800r/min, and the time is scattered in the mixed solution of water and ethanol for 50min, and water is 1 with the mass ratio of ethanol:
8；The concentration of α-ZrP is 0.02g/ml after dispersion；
2) reaction of small molecule ethamine is added, ethamine is 1 with the mol ratio of α-ZrP:4.0, add ethamine reaction time be
1.8h；
3) silane coupler 3- aminopropyls-trimethoxy silane (APTMS) is added dropwise again to continue to react；The dropwise addition of APTMS
Amount is 2.0 with the mass ratio of α-ZrP:1；Drop rate is 1.5ml/min；The time for continuing to react is 8h；
4) solid product separating, washing and drying can obtain modified α-ZrP, and solid product separates use with solvent
Rotary Evaporators；Washing is first to soak 36h with the mixed solution of water in the acetone that concentration is 98%, clear with a large amount of acetone solns afterwards
5 times are washed up to the reaction raw materials of noresidue in product；Dry to be placed in vacuum drying oven, 80 DEG C, under the conditions of vacuum 0.1MPa
Drying 36h；
5) modified α-ZrP bakee 10min under the conditions of 320 DEG C, that is, obtain organically-modified α-ZrP, and the organically-modified α-
ZrP outward appearances are white powder, and are lamellar compound, and the interlamellar spacing of the organically-modified α-ZrP is 1.84nm (2 θ=4.80 °)；
Organically-modified α-the ZrP are made up of α-ZrP and silane coupler 3- aminopropyls-trimethoxy silane (APTMS), and APTMS is inserted
In α-ZrP interlayers, grafting rates of the APTMS on α-ZrP is 9.62%, and organically-modified α-ZrP initial decomposition temperatures are 356 DEG C；
Organically-modified α-ZrP can be dispersed in non-polar organic solvent n-hexane；
6) PET is dried into 6h at 150 DEG C, then by 3- aminopropyls-trimethoxy silane (APTMS) intercalation α-ZrP with
PET is according to 30:70 (W/W) double screw extruders melt blending, granulation at a temperature of 265 DEG C, obtain amino containing 30%3-
The PET master batch material of propyl-trimethoxysilane (APTMS) intercalation α-ZrP；
7) it is 2% by the weight/mass percentage composition of α-ZrP in end article is set, above-mentioned 3- aminopropyls-trimethoxy will be contained
The PET master batch of base silane (APTMS) intercalation α-ZrP is well mixed with PET, then dries 6h at 160 DEG C, is used at 285 DEG C
Injection obtains the modified PET pieces of organic α-ZrP on injection machine.
Through inspection, the final α-ZrP contents of the plastic sheet that the present embodiment is obtained are 2.26%, and light transmittance is super in visible region
72% is crossed, is more than the 85% of pure PET；Final OTR oxygen transmission rate reduction about 28%；Permeability rate reduction by 44%.The technique can be used for
Prepare heparin tube, beer bottle and the cosmetics container containing raw material of good barrier property.
Embodiment three
A kind of preparation method of PET- organic intercalations α-ZrP composites, comprises the following steps：
1) by α-ZrP at ambient temperature, ultrasound and mechanical agitation, ultrasonic power is 60W, and the time is 30min；Machinery is stirred
The rotating speed mixed is 500r/min, and the time is scattered in the mixed solution of water and ethanol for 30min, and water is 1 with the mass ratio of ethanol:
5；The concentration of α-ZrP is 0.008g/ml after dispersion；
2) reaction of small molecule n-propylamine is added, n-propylamine is 1 with the mol ratio of α-ZrP:2.2, add n-propylamine reaction
Time is 0.9h；
3) silane coupler γ-methyl-acryloyloxy-propyl-trimethoxysilane (MPMS) is added dropwise again to continue to react；
The dripping quantity of MPMS is 1.0 with the mass ratio of α-ZrP:1；Drop rate is 1.2ml/min；The time for continuing to react is 5h；
4) solid product separating, washing and drying can obtain modified α-ZrP, and solid product separates use with solvent
Rotary Evaporators；Washing is first to soak 28h with the mixed solution of water in the acetone that concentration is 92%, clear with a large amount of acetone solns afterwards
4 times are washed up to the reaction raw materials of noresidue in product；Dry to be placed in vacuum drying oven, 65 DEG C, under the conditions of vacuum 0.06MPa
Drying 28h；
5) modified α-ZrP bakee 5min under the conditions of 260 DEG C, that is, obtain organically-modified α-ZrP, and the organically-modified α-
ZrP outward appearances are white powder, and are lamellar compound, the interlamellar spacing 1.81nm (2 θ=4.86 °) of the organically-modified α-ZrP；Should
Organically-modified α-ZrP are by α-ZrP and silane coupler γ-methyl-acryloyloxy-propyl-trimethoxysilane (MPMS) group
Into MPMS is inserted in α-ZrP interlayers, and grafting rates of the MPMS on α-ZrP is 10.28%, organically-modified α-ZrP initial decomposition temperatures
It is 364 DEG C；Organically-modified α-ZrP can be dispersed in non-polar organic solvent n-hexane；
6) PET is dried into 4h at 180 DEG C, then by γ-methyl-acryloyloxy-propyl-trimethoxysilane (MPMS)
Intercalation α-ZrP and PET is according to 40:60 (W/W) double screw extruders melt blending, granulation at a temperature of 285 DEG C, are contained
The PET master batch material of 40% γ-methyl-acryloyloxy-propyl-trimethoxysilane (MPMS) intercalation α-ZrP；
7) it is 5% by the weight/mass percentage composition of α-ZrP in end article is set, above-mentioned γ-methyl-propen acyl-oxygen will be contained
The PET master batch of base-propyl-trimethoxysilane (MPMS) intercalation α-ZrP is well mixed with PET, is then dried at 180 DEG C
8h, the modified PET pieces of organic α-ZrP are obtained at 300 DEG C with injection on injection machine.
Through inspection, the final α-ZrP contents of the plastic sheet that the present embodiment is obtained are 5.34%, and light transmittance is super in visible region
75% is crossed, is more than the 89% of pure PET；Final OTR oxygen transmission rate reduction about 32%；Permeability rate reduction by 52%.The technique can be used for
Prepare heparin tube, beer bottle and the cosmetics container containing raw material of good barrier property.
Example IV
A kind of preparation method of PET- organic intercalations α-ZrP composites, comprises the following steps：
1) by α-ZrP at ambient temperature, ultrasound and mechanical agitation, ultrasonic power is 60W, and the time is 25min；Machinery is stirred
The rotating speed mixed is 500r/min, and the time is scattered in the mixed solution of water and ethanol for 30min, and water is 1 with the mass ratio of ethanol:
5；The concentration of α-ZrP is 0.01g/ml after dispersion；
2) reaction of small molecule methylamine is added, methylamine is 1 with the mol ratio of α-ZrP:3.0, add methylamine reaction time be
1.5h；
3) silane coupler γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560) is added dropwise again to continue to react；KH-
560 dripping quantity is 1.5 with the mass ratio of α-ZrP:1；Drop rate is 1.1ml/min；The time for continuing to react is 5h；
4) solid product separating, washing and drying can obtain modified α-ZrP, and solid product separates use with solvent
Rotary Evaporators；Washing is first to soak 30h with the mixed solution of water in the acetone that concentration is 92%, clear with a large amount of acetone solns afterwards
4 times are washed up to the reaction raw materials of noresidue in product；Dry to be placed in vacuum drying oven, 66 DEG C, under the conditions of vacuum 0.08MPa
Drying 30h；
5) modified α-ZrP bakee 6min under the conditions of 300 DEG C, that is, obtain organically-modified α-ZrP, and the organically-modified α-
ZrP outward appearances are white powder, and are lamellar compound, and interlamellar spacing is 1.76nm (2 θ=5.00 °)；Organically-modified α-the ZrP by
α-ZrP and silane coupler γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560) composition, KH-560 are inserted in α-ZrP
Interlayer, grafting rates of the KH-560 on α-ZrP is 11.26%, and organically-modified α-ZrP initial decomposition temperatures are 376 DEG C；It is organic to change
Property α-ZrP can be dispersed in non-polar organic solvent n-hexane；
6) PET is dried into 5h at 130 DEG C, then inserts γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560)
Layer α-ZrP and PET is according to 50:50 (W/W) double screw extruders melt blending, granulation at a temperature of 300 DEG C, are contained
The PET master batch material of 50% γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560) intercalation α-ZrP；
7) it is 8% by the weight/mass percentage composition of α-ZrP in end article is set, above-mentioned γ-glycidyl ether oxygen third will be contained
The PET master batch of base trimethoxy silane (KH-560) intercalation α-ZrP is well mixed with PET, then dries 4h at 120 DEG C,
At 330 DEG C the modified PET pieces of organic α-ZrP are obtained with injection on injection machine.
Through inspection, the final α-ZrP contents of the plastic sheet that the present embodiment is obtained are 8.52%, and light transmittance is super in visible region
78% is crossed, is the 92% of pure PET；Final OTR oxygen transmission rate reduction about 35%；Permeability rate reduction by 57%.The technique can be used to prepare
The heparin tube of good barrier property.
Embodiment five
A kind of preparation method of PET- organic intercalations α-ZrP composites, comprises the following steps：
1) by α-ZrP at ambient temperature, ultrasound and mechanical agitation, ultrasonic power is 60W, and the time is 35min；Machinery is stirred
The rotating speed mixed is 650r/min, and the time is scattered in the mixed solution of water and ethanol for 25min, and water is 1 with the mass ratio of ethanol:
6；The concentration of α-ZrP is 0.009g/ml after dispersion；
2) reaction of small molecule ethamine is added, ethamine is 1 with the mol ratio of α-ZrP:2.5, add ethamine reaction time be
0.9h；
3) silane coupler isocyanates propyl-triethoxysilicane (IPTS) is added dropwise again to continue to react；The dripping quantity of IPTS
It is 1.2 with the mass ratio of α-ZrP:1；Drop rate is 0.6ml/min；The time for continuing to react is 7h；
4) solid product separating, washing and drying can obtain modified α-ZrP, and solid product separates use with solvent
Rotary Evaporators；Washing is first to soak 26h with the mixed solution of water in the acetone that concentration is 96%, clear with a large amount of acetone solns afterwards
5 times are washed up to the reaction raw materials of noresidue in product；Dry to be placed in vacuum drying oven, 66 DEG C, under the conditions of vacuum 0.07MPa
Drying 32h；
5) modified α-ZrP bakee 5min under the conditions of 280 DEG C, that is, obtain organically-modified α-ZrP, and the organically-modified α-
ZrP outward appearances are white powder, and are lamellar compound, and interlamellar spacing is 1.65nm (2 θ=5.34 °)；Organically-modified α-the ZrP by
α-ZrP and silane coupler isocyanates propyl-triethoxysilicane (IPTS) are constituted, and IPTS is inserted in α-ZrP interlayers, and IPTS exists
Grafting rate on α-ZrP is 12.19%, and organically-modified α-ZrP initial decomposition temperatures are 374 DEG C；Organically-modified α-ZrP can be equal
It is even to be dispersed in non-polar organic solvent n-hexane；
6) PET is dried into 7h at 170 DEG C, then by isocyanates propyl-triethoxysilicane (IPTS) intercalation α-ZrP with
PET is according to 30:70 (W/W) double screw extruders melt blending, granulation at a temperature of 280 DEG C, obtain containing 30% isocyanic acid
The PET master batch material of ester propyl-triethoxysilicane (IPTS) intercalation α-ZrP；
7) it is 10% by the weight/mass percentage composition of α-ZrP in end article is set, the above-mentioned second of isocyanates propyl group three will be contained
The PET master batch of TMOS (IPTS) intercalation α-ZrP is well mixed with PET, then dries 7h at 170 DEG C, is used at 290 DEG C
Injection obtains the modified PET pieces of organic α-ZrP on injection machine.
Through inspection, the final α-ZrP contents of the plastic sheet that the present embodiment is obtained are 9.34%, and light transmittance is super in visible region
80% is crossed, is more than the 95% of pure PET；Final OTR oxygen transmission rate reduction about 38%；Permeability rate reduction by 61%.The technique can be used for
Prepare heparin tube, beer bottle and the cosmetics container containing raw material of good barrier property.
Claims (10)
1. a kind of preparation method of PET- organic intercalations α-ZrP composites, it is characterised in that comprise the following steps：
1) α-ZrP are scattered in the mixed solution of water and ethanol；
2) small molecule amine reaction is added；
3) silane coupler is added dropwise again to continue to react；
4) solid product separating, washing and drying can obtain modified α-ZrP；
5) the modified α-ZrP are processed under the conditions of 250~320 DEG C, that is, obtain organically-modified α-ZrP；
6) the organically-modified α-ZrP and abundant dry PET are pressed 20:80~80:20 weight obtains mixture than mixing
Material, the mixed material of abundant dry PET and organic intercalation α-ZrP is first mixed with banbury, then existed with double screw extruder
Melt blending, granulation, obtain the PET master batch of-ZrP of α containing organic intercalation at a temperature of 245~300 DEG C；
7) by step 6) PET master batch of the obtained-ZrP of α containing organic intercalation and PET be well mixed so that there is the machine transplanting of rice in mixture
The mass percent of layer α-ZrP is 1~10%, then uses injection machine injection moulding, obtains the PET- organic intercalations α-ZrP multiple
Condensation material, the light transmittance of the PET- organic intercalation α-ZrP composites, more than 65~82%, is the 77 of pure PET in visible region
~97%, OTR oxygen transmission rate reduction by 20~40%；Permeability rate reduction by 35~65%.
2. the preparation method of PET- organic intercalations α-ZrP composites according to claim 1, it is characterised in that step
1) in, the mixed solution of the water and ethanol, water is 1 with the mass ratio of ethanol:2~1:8；The concentration of α-ZrP is after dispersion
0.005~0.02g/ml；The dispersion refers to ultrasonic and mechanical agitation at ambient temperature；Churned mechanically rotating speed be 200~
800r/min, the time is 20~50min；The ultrasound refers to that at ambient temperature, ultrasonic power is 50-90W, the time is 20~
50min。
3. the preparation method of PET- organic intercalations α-ZrP composites according to claim 1, it is characterised in that small point
Sub- amine is 1 with the mol ratio of α-ZrP:2.0~1:4.0, the time for adding small molecule amine reaction is 0.6~1.8h；Described small point
Sub- amine is methylamine, ethamine or n-propylamine.
4. the preparation method of PET- organic intercalations α-ZrP composites according to claim 1, it is characterised in that silane
The dripping quantity of coupling agent is 0.5 with the mass ratio of α-ZrP:1~2.0:1；Drop rate is 0.1~1.5ml/min；The continuation
The time of reaction is 3~8h；The silane coupler is 3- aminopropyls-triethoxysilane, 3- aminopropyls-trimethoxy
Silane or γ-methyl-acryloyloxy-propyl-trimethoxysilane.
5. the preparation method of PET- organic intercalations α-ZrP composites according to claim 1, it is characterised in that step
4) in, solid product is separated with solvent and uses Rotary Evaporators；The washing is first in the acetone and water that concentration is 90~98%
Mixed solution soak 24~36h, 3~5 reaction raw materials of the noresidue in the product are cleaned with a large amount of acetone solns afterwards；Institute
Drying is stated to be placed in vacuum drying oven, 60~80 DEG C, 24~36h is dried under the conditions of 0.05~0.1MPa of vacuum；Step 5) in,
The treatment refers to that modified α-ZrP are bakeed into 3~10min under the conditions of 250~320 DEG C.
6. the preparation method of the PET- organic intercalation α-ZrP composites according to any one of Claims 1 to 5, it is special
Levy and be, the organically-modified α-ZrP outward appearances are white powder；Organically-modified α-the ZrP are lamellar compound, and interlamellar spacing is
1.60~1.90nm；Organically-modified α-the ZrP are made up of α-ZrP and silane coupler, and silane coupler is inserted in α-ZrP layers
Between, grafting rate of the silane coupler on α-ZrP is 6~18%；Organically-modified α-ZrP the initial decomposition temperatures be 340~
400℃；Organically-modified α-the ZrP can be dispersed in non-polar organic solvent n-hexane.
7. the preparation method of PET- organic intercalations α-ZrP composites according to claim 1, it is characterised in that step
6) in, the fully dry PET is that 4~8h is dried at a temperature of 120~180 DEG C.
8. the preparation method of PET- organic intercalations α-ZrP composites according to claim 1, it is characterised in that described
The weight/mass percentage composition of organic intercalation α-ZrP is 20~80% in the PET master batch of-ZrP of α containing organic intercalation.
9. the preparation method of PET- organic intercalations α-ZrP composites according to claim 1, it is characterised in that step
7) in, 4~8h is first dried after the PET master batch and PET of the-ZrP of α containing organic intercalation are well mixed at a temperature of 120~180 DEG C,
It is molded with injection machine again.
10. the preparation method of PET- organic intercalations α-ZrP composites according to claim 1, it is characterised in that step
7) in, the PET master batch of-ZrP of α containing organic intercalation and the mixture of PET are molded at a temperature of 265~330 DEG C with injection machine；System
The PET- organic intercalations α-ZrP composites in organic intercalation α-ZrP account for the weight/mass percentage composition of composite for 1~
10%.
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