CN107353567A - TPE/PVB composite fresh-keeping lids and preparation method thereof - Google Patents
TPE/PVB composite fresh-keeping lids and preparation method thereof Download PDFInfo
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- CN107353567A CN107353567A CN201710468259.2A CN201710468259A CN107353567A CN 107353567 A CN107353567 A CN 107353567A CN 201710468259 A CN201710468259 A CN 201710468259A CN 107353567 A CN107353567 A CN 107353567A
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- hydrothermal product
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a kind of TPE/PVB composite fresh-keepings lid and preparation method thereof, the preparation method includes：1) aluminum soluble salt, soluble magnesium salt, soluble zirconates, urea and water are mixed and made into salting liquid, then carry out hydro-thermal reaction so that hydrothermal product is made；2) hydrothermal product is carried out to ball milling in silane coupler so that modified hydrothermal product is made；3) TPE (thermoplastic elastomer), PVB (polyvinyl butyral resin), kaolin, stearic acid, paraffin oil, diisononyl phthalate, silicon powder, modified hydrothermal product and oleic acid are kneaded, are molded so that TPE/PVB composite fresh-keeping lids are made.The TPE/PVB composite fresh-keeping lids have an excellent resistance to elevated temperatures, while the preparation method has process simple and the advantages of raw material is easy to get.
Description
Technical field
The present invention relates to fresh-keeping box cover, in particular it relates to TPE/PVB composite fresh-keeping lids and preparation method thereof.
Background technology
Fresh-keeping box cover is the important composition component of crisper, and it not only determines the sealing property of crisper, while also straight
Connecing influences the fresh keeping property of crisper.At present, fresh-keeping box cover is mainly that macromolecule is made, and disclosure satisfy that the market demand substantially, but
It is in use, often to find at once to seal crisper after high temperature food is contained, no person can lead
The deformation of crisper is caused, it can thus be appreciated that still having certain shortcoming in the resistance to elevated temperatures of current fresh-keeping box cover.
The content of the invention
It is an object of the invention to provide a kind of TPE/PVB composite fresh-keepings lid and preparation method thereof, the compound guarantors of the TPE/PVB
Fresh lid has an excellent resistance to elevated temperatures, while the preparation method has process simple and the advantages of raw material is easy to get.
To achieve these goals, the invention provides a kind of preparation method of TPE/PVB composite fresh-keepings lid, including：
1) aluminum soluble salt, soluble magnesium salt, soluble zirconates, urea and water are mixed and made into salting liquid, then carried out
Hydro-thermal reaction is with obtained hydrothermal product；
2) hydrothermal product is carried out to ball milling in silane coupler so that modified hydrothermal product is made；
3) by TPE (thermoplastic elastomer), PVB (polyvinyl butyral resin), kaolin, stearic acid, paraffin oil, O-phthalic
Sour dinonyl, silicon powder, modified hydrothermal product and oleic acid are kneaded, are molded so that TPE/PVB composite fresh-keeping lids are made.
Present invention also offers a kind of TPE/PVB composite fresh-keepings lid, the TPE/PVB composite fresh-keeping lids pass through above-mentioned
Preparation method is prepared.
In the above-mentioned technical solutions, the present invention passes through aluminum soluble salt, soluble magnesium salt, soluble zirconates, urea first
Aluminum hydroxide/magnesium zirconium compounds is generated with the hydro-thermal reaction of water；Then can be by by the surface of the ball milling hydroxide
Activation produces free radical or ion, so as to be preferably coupled with silane coupler, improves its lipophilic-hydrophobic property；Finally lead to
Cross modified hydrothermal product and obtain resistance to elevated temperatures as fresh-keeping box cover made from fire retardant raising.Meanwhile the preparation method has work
The advantages of sequence is simply and raw material is easy to get.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of preparation method of TPE/PVB composite fresh-keepings lid, including：
1) aluminum soluble salt, soluble magnesium salt, soluble zirconates, urea and water are mixed and made into salting liquid, then carried out
Hydro-thermal reaction is with obtained hydrothermal product；
2) hydrothermal product is carried out to ball milling in silane coupler so that modified hydrothermal product is made；
3) by TPE (thermoplastic elastomer), PVB (polyvinyl butyral resin), kaolin, stearic acid, paraffin oil, O-phthalic
Sour dinonyl, silicon powder, modified hydrothermal product and oleic acid are kneaded, are molded so that TPE/PVB composite fresh-keeping lids are made.
In the step 1) of above-mentioned preparation method, the dosage of each material can select in wide scope, but in order to enter
One step improve made from fresh-keeping box cover resistance to elevated temperatures, it is preferable that in step 1), relative to 1mmol aluminum soluble salt,
The dosage of soluble magnesium salt is 0.5-0.8mmol, and the dosage of soluble zirconates is 0.1-0.3mmol, and the dosage of urea is 3-
5mmol, the dosage of water is 5-10mL.
In the step 1) of above-mentioned preparation method, aluminum soluble salt, soluble magnesium salt, the specific species of soluble zirconates can
To be selected in wide scope, but in order to further improve the resistance to elevated temperatures of obtained fresh-keeping box cover, it is preferable that in step
1) in, aluminum soluble salt is selected from least one of aluminium chloride, aluminum nitrate or aluminum sulfate, and soluble magnesium salt is selected from magnesium chloride
And/or in magnesium nitrate, soluble zirconates is selected from zirconium chloride and/or zirconium nitrate.
In the step 1) of above-mentioned preparation method, the actual conditions of hydro-thermal reaction can select in wide scope, still
In order to further improve the resistance to elevated temperatures of obtained fresh-keeping box cover, it is preferable that in step 1), hydro-thermal reaction at least meet with
Lower condition：Carried out in closed environment, reaction temperature is 170-200 DEG C, reaction time 12-20h.
In the step 2) of above-mentioned preparation method, the dosage of each material can select in wide scope, but in order to enter
One step improve made from fresh-keeping box cover resistance to elevated temperatures, it is preferable that in step 2), hydrothermal product and silane coupler rub
You are than being 1：0.1-0.2.
In the step 2) of above-mentioned preparation method, the specific species of silane coupler can select in wide scope, but
It is to further improve the resistance to elevated temperatures of obtained fresh-keeping box cover, it is preferable that in step 2), silane coupler is selected from silicon
At least one of alkane coupling agent Kh550, silane coupler Kh560 and silane coupler Kh570.
In the step 2) of above-mentioned preparation method, the actual conditions of ball milling can select in wide scope, but in order to
The resistance to elevated temperatures of fresh-keeping box cover made from further improving, it is preferable that in step 2), ball milling at least meets following condition：
The number ratio of big ball and bead is 2：The mass ratio of 0.8-1.2, abrading-ball and material is 10：2-2.5, rotating speed 800-1000rpm,
Ball-milling Time is 40-60min.
In the step 3) of above-mentioned preparation method, the dosage of each material can select in wide scope, but in order to enter
The resistance to elevated temperatures of fresh-keeping box cover made from the raising of one step, it is preferable that in step 3), TPE, PVB, kaolin, stearic acid, stone
Wax oil, diisononyl phthalate, silicon powder, the weight ratio of modified hydrothermal product and oleic acid are 100：30-38：20-27：
18-24：7-18：22-37：4-7：6-10：30-38.
In the step 3) of above-mentioned preparation method, it is kneaded and the condition of shaping can selects in wide scope, still
In order to further improve the resistance to elevated temperatures of obtained fresh-keeping box cover, it is preferable that in step 3), mixing at least meets following bar
Part：Melting temperature is 200-215 DEG C, mixing time 4-6h；Shaping is carried out by the way of extrusion molding.
In the step 3) of above-mentioned preparation method, TPE specific species can select in wide scope, but in order to enter
The resistance to elevated temperatures of fresh-keeping box cover, TPE are selected from SBS (SB), TPU (thermoplasticity made from the raising of one step
Polyurethane), at least one of TEO (polyolefin thermoplastic elastomer) and TES (styrenic thermoplastic elastomer).
Present invention also offers a kind of TPE/PVB composite fresh-keepings lid, the TPE/PVB composite fresh-keeping lids pass through above-mentioned
Preparation method is prepared.
The present invention will be described in detail by way of examples below.
Embodiment 1
1) by aluminum soluble salt (aluminium chloride), soluble magnesium salt (magnesium chloride), soluble zirconates (zirconium chloride), urea and water
According to 1mmol：0.6mmol：0.2mmol：4mmol：8mL amount ratio carries out being mixed and made into salting liquid, then the water at 180 DEG C
Thermal response 16h is with obtained hydrothermal product；
2) by hydrothermal product, silane coupler (silane coupler Kh550) according to 1：It is (big that 0.15 mol ratio carries out ball milling
The number of ball and bead ratio is 2：1, the mass ratio of abrading-ball and material is 10：2.3, rotating speed 900rpm, Ball-milling Time are
50min) hydrothermal product is modified to be made；
3) by TPE (SBS), PVB, kaolin, stearic acid, paraffin oil, diisononyl phthalate, silicon powder, modification
Hydrothermal product and oleic acid are according to 100：35：24：20：15：28：6：8：35 weight ratio be kneaded at 210 DEG C 5h, extrusion molding with
TPE/PVB composite fresh-keeping lids A1 is made.
Embodiment 2
1) by aluminum soluble salt (aluminum nitrate), soluble magnesium salt (magnesium nitrate), soluble zirconates (zirconium nitrate), urea and water
According to 1mmol：0.5mmol：0.1mmol：3mmol：5mL amount ratio carries out being mixed and made into salting liquid, then the water at 170 DEG C
Thermal response 12h is with obtained hydrothermal product；
2) by hydrothermal product, silane coupler (silane coupler Kh560) according to 1：It is (big that 0.1 mol ratio carries out ball milling
The number of ball and bead ratio is 2：0.8, the mass ratio of abrading-ball and material is 10：2, rotating speed 800rpm, Ball-milling Time are
40min) hydrothermal product is modified to be made；
3) by TPE (TEO), PVB, kaolin, stearic acid, paraffin oil, diisononyl phthalate, silicon powder, modification
Hydrothermal product and oleic acid are according to 100：30：20：18：7：22：4：6：30 weight ratio be kneaded at 200 DEG C 4h, extrusion molding with
TPE/PVB composite fresh-keeping lids A2 is made.
Embodiment 3
1) by aluminum soluble salt (aluminum sulfate), soluble magnesium salt (magnesium nitrate), soluble zirconates (zirconium nitrate), urea and water
According to 1mmol：0.8mmol：0.3mmol：5mmol：10mL amount ratio carries out being mixed and made into salting liquid, then at 200 DEG C
Hydro-thermal reaction 20h is with obtained hydrothermal product；
2) by hydrothermal product, silane coupler (silane coupler Kh570) according to 1：It is (big that 0.2 mol ratio carries out ball milling
The number of ball and bead ratio is 2：1.2, the mass ratio of abrading-ball and material is 10：2.5, rotating speed 1000rpm, Ball-milling Time are
60min) hydrothermal product is modified to be made；
3) by TPE (TES), PVB, kaolin, stearic acid, paraffin oil, diisononyl phthalate, silicon powder, modification
Hydrothermal product and oleic acid are according to 100：38：27：24：18：37：7：10：38 weight ratio is kneaded 6h, extrusion molding at 215 DEG C
So that TPE/PVB composite fresh-keeping lids A3 is made.
Comparative example 1
Method according to embodiment 1 carries out that fresh-keeping box cover B1 is made, unlike, soluble aluminum is not used in step 1)
Salt.
Comparative example 2
Method according to embodiment 1 carries out that fresh-keeping box cover B2 is made, unlike, soluble magnesium is not used in step 1)
Salt.
Comparative example 3
Method according to embodiment 1 carries out that fresh-keeping box cover B3 is made, unlike, soluble zirconium is not used in step 1)
Salt.
Comparative example 4
Method according to embodiment 1 carries out that fresh-keeping box cover B4 is made, unlike, it is not used in step 2) silane coupled
Agent.
Comparative example 5
Method according to embodiment 1 carries out that fresh-keeping box cover B5 is made, unlike, modified hydro-thermal production is not used in step 3)
Thing.
Detect example 1
The method recorded according to GB1035-70 detects the heat distortion temperature of above-mentioned fresh-keeping box cover, and concrete outcome is shown in Table 1.
Table 1
| Heat distortion temperature/DEG C | |
| A1 | 298 |
| A2 | 289 |
| A3 | 290 |
| B1 | 265 |
| B2 | 250 |
| B3 | 257 |
| B4 | 249 |
| B5 | 220 |
There is excellent resistance to height by above-described embodiment, comparative example and detection example, fresh-keeping box cover provided by the invention
Warm nature energy.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
- A kind of 1. preparation method of TPE/PVB composite fresh-keepings lid, it is characterised in that including：1) aluminum soluble salt, soluble magnesium salt, soluble zirconates, urea and water are mixed and made into salting liquid, then carry out hydro-thermal Reaction is with obtained hydrothermal product；2) hydrothermal product is carried out to ball milling in silane coupler so that modified hydrothermal product is made；3) by TPE (thermoplastic elastomer), PVB (polyvinyl butyral resin), kaolin, stearic acid, paraffin oil, phthalic acid two Different nonyl ester, silicon powder, modified hydrothermal product and oleic acid are kneaded, are molded so that the TPE/PVB composite fresh-keepings lid is made.
- 2. preparation method according to claim 1, wherein, in step 1), relative to the 1mmol soluble aluminum Salt, the dosage of the soluble magnesium salt are 0.5-0.8mmol, and the dosage of the soluble zirconates is 0.1-0.3mmol, the urine The dosage of element is 3-5mmol, and the dosage of the water is 5-10mL.
- 3. preparation method according to claim 1, wherein, in step 1), the aluminum soluble salt is selected from aluminium chloride, nitre At least one of sour aluminium or aluminum sulfate, the soluble magnesium salt is in magnesium chloride and/or magnesium nitrate, the soluble zirconium Salt is selected from zirconium chloride and/or zirconium nitrate.
- 4. preparation method according to claim 1, wherein, in step 1), the hydro-thermal reaction at least meets following bar Part：Carried out in closed environment, reaction temperature is 170-200 DEG C, reaction time 12-20h.
- 5. according to the preparation method described in any one in claim 1-4, wherein, in step 2), the hydrothermal product with The mol ratio of silane coupler is 1：0.1-0.2.
- 6. preparation method according to claim 5, wherein, in step 2), the silane coupler is selected from silane coupled At least one of agent Kh550, silane coupler Kh560 and silane coupler Kh570.
- 7. preparation method according to claim 5, wherein, in step 2), the ball milling at least meets following condition：Greatly The number of ball and bead ratio is 2：The mass ratio of 0.8-1.2, abrading-ball and material is 10：2-2.5, rotating speed 800-1000rpm, ball Consume time as 40-60min.
- 8. the preparation method according to claim 6 or 7, wherein, in step 3), the TPE, PVB, kaolin, tristearin Acid, paraffin oil, diisononyl phthalate, silicon powder, the weight ratio of modified hydrothermal product and oleic acid are 100：30-38：20- 27：18-24：7-18：22-37：4-7：6-10：30-38.
- 9. preparation method according to claim 8, wherein, in step 3), the mixing at least meets following condition：It is mixed It is 200-215 DEG C to refine temperature, mixing time 4-6h；The shaping is carried out by the way of extrusion molding；Preferably, the TPE is selected from SBS (SB), TPU (thermoplastic polyurethane), TEO (polyolefin heat At least one of plastics elastomer) and TES (styrenic thermoplastic elastomer).
- 10. a kind of TPE/PVB composite fresh-keepings lid, it is characterised in that the TPE/PVB composite fresh-keepings lid passes through claim Preparation method in 1-9 described in any one is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710468259.2A CN107353567A (en) | 2017-06-20 | 2017-06-20 | TPE/PVB composite fresh-keeping lids and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710468259.2A CN107353567A (en) | 2017-06-20 | 2017-06-20 | TPE/PVB composite fresh-keeping lids and preparation method thereof |
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| CN107353567A true CN107353567A (en) | 2017-11-17 |
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| CN201710468259.2A Pending CN107353567A (en) | 2017-06-20 | 2017-06-20 | TPE/PVB composite fresh-keeping lids and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051017A (en) * | 2009-11-09 | 2011-05-11 | 赢创德固赛有限公司 | Thermoplastic elastomer mixtures |
| CN103540075A (en) * | 2012-07-18 | 2014-01-29 | 苏州朗创化工有限公司 | Highly flame-retardant TPE (Thermoplastic Polyurethane Elastomer) material |
-
2017
- 2017-06-20 CN CN201710468259.2A patent/CN107353567A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051017A (en) * | 2009-11-09 | 2011-05-11 | 赢创德固赛有限公司 | Thermoplastic elastomer mixtures |
| CN103540075A (en) * | 2012-07-18 | 2014-01-29 | 苏州朗创化工有限公司 | Highly flame-retardant TPE (Thermoplastic Polyurethane Elastomer) material |
Non-Patent Citations (3)
| Title |
|---|
| 唐玉菲等: "水滑石的结构特性及作为塑料助剂的应用", 《化工科技》 * |
| 朱建等: "尿素水热法制备锌镁铝多元水滑石及形成机理", 《无机盐工业》 * |
| 申延明: "含Pd_Cu_Ni_Zr类水滑石的合成及其催化应用", 《中国博士学位论文全文数据库 工程技术Ι辑》 * |
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Application publication date: 20171117 |