CN104194160A - Polypropylene film covering material and preparation method thereof - Google Patents
Polypropylene film covering material and preparation method thereof Download PDFInfo
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- CN104194160A CN104194160A CN201410493619.0A CN201410493619A CN104194160A CN 104194160 A CN104194160 A CN 104194160A CN 201410493619 A CN201410493619 A CN 201410493619A CN 104194160 A CN104194160 A CN 104194160A
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/549—Silicon-containing compounds containing silicon in a ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- 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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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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
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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Abstract
The invention provides plypropylene film covering material. The plypropylene film covering material is formed by performing irradiation crosslinking on polysilsesquioxane containing terminal alkenyl, polypropylene and antioxidant. By performing irradiation crosslinking on polysilsesquioxane containing terminal alkenyl and polypropylene, the surface texture of plypropylene film covering material obtained can be completely kept, and the mechanical property of the plypropylene film covering material obtained is good; in addition, as polysilsesquioxane containing terminal alkenyl is taken as a crosslinking agent accelerant, the residual crosslinking agent in the lypropylene film covering material prepared cannot be slowly separated out during later use, and the stability of the plypropylene film covering material is improved.
Description
Technical field
The present invention relates to technical field of macromolecules, further relate to a kind of polypropylene covering material and preparation method thereof.
Background technology
Polypropylene is a kind of environmentally friendly macromolecular material, there is excellent mechanical property, electrical property, chemical proofing, be widely used in the manufacture of the products such as inner and outer decorative parts of automobile, daily necessities, finishing material, wrapping material, electronic apparatus, weaving, medical apparatus; Because Properties of Polypropylene is good, mature production technology, with low cost, become one of macromolecular material that growth is the fastest, output is the highest at present.
In recent years, the application of polypropylene material expands to overlay film product scope gradually, as the surface coating of the products such as automotive upholstery, furniture, finishing material.Compare with conventional similar covering material flexible PVC, polyacrylic heat resisting temperature, hardness, scratch resistant performance are better, what is more important, polypropylene covering material does not need to add softening agent in moulding process, greatly simplified complete processing, and in the use procedure in later stage, can be because slowly separating out of softening agent produces toxicity yet.
But, polypropylene covering material is by plastic uptake technique and substrate is adhesion-molded while becoming inside gadget, furniture, decorative product, and because heat resisting temperature is not enough, its superficial makings or pattern easily produce distortion or disappear at plastic uptake temperature, be difficult to retain completely, affect product appearance.At present, also there is the heat-resisting polypropylene covering material of researchist's polypropylene and crosslinking accelerator preparation as crosslinked in mixed radiations such as TAIC, TMPTA, TPGDA, PETA, yet, because auto-polymerization and partial cross-linked dose can occur these crosslinking accelerators in irradiation process, do not react, make the stability of the polypropylene covering material that obtains not high, have a strong impact on the work-ing life in its later stage.
Summary of the invention
In view of this, technical problem to be solved by this invention is to provide a kind of polypropylene covering material and preparation method thereof, and during polypropylene covering material provided by the invention was used in the later stage, stability is high, and in moulding process, can make superficial makings retain completely.
The invention provides a kind of polypropylene covering material, by containing, hold poly organic silicon sesquioxyalkane, polypropylene and the antioxidant of thiazolinyl to make through cross-linking radiation.
Preferably, described in, contain and hold the poly organic silicon sesquioxyalkane of thiazolinyl for thering is the T of formula (I) structure
8cage modle poly organic silicon sesquioxyalkane, there is the T of formula (II) structure
10cage modle poly organic silicon sesquioxyalkane and the T with formula (III) structure
12one or more in cage modle poly organic silicon sesquioxyalkane,
formula (I),
formula (II),
formula (III),
Described R
1-1, R
2-1, R
3-1, R
4-1, R
5-1, R
6-1, R
7-1, R
8-1independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, wherein, R
1-1, R
2-1, R
3-1, R
4-1, R
5-1, R
6-1, R
7-1and R
8-1in have at least two groups be selected from C1～C15 containing end thiazolinyl unsaturated alkyl;
Described R
1-2, R
2-2, R
3-2, R
4-2, R
5-2, R
6-2, R
7-2, R
8-2, R
9-2, R
10-2independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, wherein, R
1-2, R
2-2, R
3-2, R
4-2, R
5-2, R
6-2, R
7-2, R
8-2, R
9-2and R
10-2in have at least two be selected from C1～C15 containing end thiazolinyl unsaturated alkyls;
Described R
1-3, R
2-3, R
3-3, R
4-3, R
5-3, R
6-3, R
7-3, R
8-3, R
9-3, R
10-3, R
11-3, R
12-3independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, wherein, R
1-3, R
2-3, R
3-3, R
4-3, R
5-3, R
6-3, R
7-3, R
8-3, R
9-3, R
10-3, R
11-3and R
12-3in have at least two be selected from C1～C15 containing end thiazolinyl unsaturated alkyls.
Preferably, described in, contain that to hold the poly organic silicon sesquioxyalkane of thiazolinyl and described polyacrylic mass ratio be (0.3～5): 100.
Preferably, described antioxidant is zinc dibutyldithiophosphate, N, one or more in N '-bis-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine and zinc dibutyl dithiocarbamate.
Preferably, described antioxidant and described polyacrylic mass ratio are (0.2～0.8): 1.
Preferably, the radiation dose of described cross-linking radiation is 10～150kGy.
The present invention also provides a kind of preparation method of polypropylene covering material, comprising:
1) by containing poly organic silicon sesquioxyalkane, polypropylene and the antioxidant blend of holding thiazolinyl, obtain blend;
2) by step 1) blend molding that obtains, irradiation, obtains polypropylene covering material.
Preferably, described in, contain that to hold the poly organic silicon sesquioxyalkane of thiazolinyl and described polyacrylic mass ratio be (0.3～5): 100.
Preferably, described in, contain and hold the poly organic silicon sesquioxyalkane of thiazolinyl for thering is the T of formula (I) structure
8cage modle poly organic silicon sesquioxyalkane, there is the T of formula (II) structure
10cage modle poly organic silicon sesquioxyalkane and the T with formula (III) structure
12one or more in cage modle poly organic silicon sesquioxyalkane,
formula (I),
formula (II),
formula (III),
Described R
1-1, R
2-1, R
3-1, R
4-1, R
5-1, R
6-1, R
7-1, R
8-1independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, wherein, R
1-1, R
2-1, R
3-1, R
4-1, R
5-1, R
6-1, R
7-1and R
8-1in have at least two groups be selected from C1～C15 containing end thiazolinyl unsaturated alkyl;
Described R
1-2, R
2-2, R
3-2, R
4-2, R
5-2, R
6-2, R
7-2, R
8-2, R
9-2, R
10-2independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, wherein, R
1-2, R
2-2, R
3-2, R
4-2, R
5-2, R
6-2, R
7-2, R
8-2, R
9-2and R
10-2in have at least two be selected from C1～C15 containing end thiazolinyl unsaturated alkyls;
Described R
1-3, R
2-3, R
3-3, R
4-3, R
5-3, R
6-3, R
7-3, R
8-3, R
9-3, R
10-3, R
11-3, R
12-3independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, wherein, R
1-3, R
2-3, R
3-3, R
4-3, R
5-3, R
6-3, R
7-3, R
8-3, R
9-3, R
10-3, R
11-3and R
12-3in have at least two be selected from C1～C15 containing end thiazolinyl unsaturated alkyls.
Preferably, the radiation dose of described cross-linking radiation is 10～150kGy.
Compared with prior art, the invention provides a kind of polypropylene covering material, by containing, hold poly organic silicon sesquioxyalkane, polypropylene and the antioxidant of thiazolinyl to make through cross-linking radiation, the present invention is by carrying out cross-linking radiation by the polypropylene that contains the poly organic silicon sesquioxyalkane of holding thiazolinyl, make the polypropylene covering material obtaining in moulding process, can make superficial makings retain completely, and the mechanical property of the polypropylene covering material obtaining is better, experimental result shows, the heat resisting temperature of covering material provided by the invention is all more than 114 ℃, the tensile strength of 100 ℃ is all more than 11MPa, in addition, because the present invention holds the poly organic silicon sesquioxyalkane of thiazolinyl as linking agent promotor using containing, in making that linking agent in polypropylene covering material that the present invention prepares is residual and can not using in the later stage, slowly separate out, improved the stability of polypropylene covering material.
Accompanying drawing explanation
Fig. 1 is the polypropylene covering material of the embodiment of the present invention 1 preparation surface topography after 120 ℃ of processing;
Fig. 2 is the polypropylene covering material of the embodiment of the present invention 2 preparation surface topography after 120 ℃ of processing;
Fig. 3 is the polypropylene covering material of the embodiment of the present invention 3 preparation surface topography after 120 ℃ of processing;
Fig. 4 is the polypropylene covering material of the embodiment of the present invention 4 preparation surface topography after 120 ℃ of processing;
Fig. 5 is the polypropylene covering material of the comparative example of the present invention 1 preparation surface topography after 120 ℃ of processing.
Embodiment
The invention provides a kind of polypropylene covering material, by containing, hold poly organic silicon sesquioxyalkane, polypropylene and the antioxidant of thiazolinyl to make through cross-linking radiation.
According to the present invention, described in contain and hold the poly organic silicon sesquioxyalkane of thiazolinyl and described polyacrylic mass ratio to be preferably (0.3～5): 100, more preferably (0.5～5): 100, most preferably be (1～3): 100; Described antioxidant and described polyacrylic mass ratio are preferably (0.2～0.8): 1, more preferably (0.3～0.6): 1, most preferably be (0.4～0.5): 1; The radiation dose of described cross-linking radiation is 10～150kGy, and more preferably 15～100kGy, most preferably is 20～50kGy.
According to the present invention, described in contain the T that holds the poly organic silicon sesquioxyalkane of thiazolinyl to be preferably to there is formula (I) structure
8cage modle poly organic silicon sesquioxyalkane, there is the T of formula (II) structure
10cage modle poly organic silicon sesquioxyalkane and the T with formula (III) structure
12one or more in cage modle poly organic silicon sesquioxyalkane, more preferably T
8cage modle poly organic silicon sesquioxyalkane, there is the T of formula (II) structure
10cage modle poly organic silicon sesquioxyalkane, there is the T of formula (III) structure
12cage modle poly organic silicon sesquioxyalkane, there is the T of formula (I) structure
8cage modle poly organic silicon sesquioxyalkane and the T with formula (II) structure
10the mixture of cage modle poly organic silicon sesquioxyalkane, there is the T of formula (I) structure
8cage modle poly organic silicon sesquioxyalkane and the T with formula (III) structure
12the mixture of cage modle poly organic silicon sesquioxyalkane, there is the T of formula (II) structure
10cage modle poly organic silicon sesquioxyalkane and the T with formula (III) structure
12the mixture of cage modle poly organic silicon sesquioxyalkane or there is the T of formula (I) structure
8cage modle poly organic silicon sesquioxyalkane, there is the T of formula (II) structure
10cage modle poly organic silicon sesquioxyalkane and the T with formula (III) structure
12the mixture of cage modle poly organic silicon sesquioxyalkane;
formula (I),
formula (II),
formula (III),
Described R
1-1, R
2-1, R
3-1, R
4-1, R
5-1, R
6-1, R
7-1, R
8-1preferably independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, more preferably independently be selected from the alkyl of C1～C6 or the unsaturated alkyl containing end thiazolinyl of C1～C10, most preferably be and be independently selected from the alkyl of C1～C4 or the unsaturated alkyl containing end thiazolinyl of C1～C6, more specifically, be independently selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, vinyl, allyl group, 3-methacrylic, 1-alkene butyl, 4-methyl isophthalic acid-alkene amyl group or 1-alkene amyl group; Wherein, described R
1-1, R
2-1, R
3-1, R
4-1, R
5-1, R
6-1, R
7-1and R
8-1in preferably have at least two groups be selected from C1～C15 containing end thiazolinyl unsaturated alkyl, more preferably have at least two groups to be selected from the unsaturated alkyl containing end thiazolinyl of C1～C10, most preferably have at least two groups to be selected from the unsaturated alkyl containing end thiazolinyl of C1～C6, more preferably have at least two groups to be selected from vinyl, allyl group, 3-methacrylic, 1-alkene butyl, 4-methyl isophthalic acid-alkene amyl group or 1-alkene amyl group;
Described R
1-2, R
2-2, R
3-2, R
4-2, R
5-2, R
6-2, R
7-2, R
8-2, R
9-2, R
10-2preferably independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, more preferably independently be selected from the alkyl of C1～C6 or the unsaturated alkyl containing end thiazolinyl of C1～C10, most preferably be and be independently selected from the alkyl of C1～C4 or the unsaturated alkyl containing end thiazolinyl of C1～C6, more specifically, be independently selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, vinyl, allyl group, 3-methacrylic, 1-alkene butyl, 4-methyl isophthalic acid-alkene amyl group or 1-alkene amyl group; Wherein, R
1-2, R
2-2, R
3-2, R
4-2, R
5-2, R
6-2, R
7-2, R
8-2, R
9-2and R
10-2in preferably have at least two groups be selected from C1～C15 containing end thiazolinyl unsaturated alkyl, more preferably have at least two groups to be selected from the unsaturated alkyl containing end thiazolinyl of C1～C10, most preferably have at least two groups to be selected from the unsaturated alkyl containing end thiazolinyl of C1～C6, more preferably have at least two groups to be selected from vinyl, allyl group, 3-methacrylic, 1-alkene butyl, 4-methyl isophthalic acid-alkene amyl group or 1-alkene amyl group;
Described R
1-3, R
2-3, R
3-3, R
4-3, R
5-3, R
6-3, R
7-3, R
8-3, R
9-3, R
10-3, R
11-3, R
12-3preferably independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, more preferably independently be selected from the alkyl of C1～C6 or the unsaturated alkyl containing end thiazolinyl of C1～C10, most preferably be and be independently selected from the alkyl of C1～C4 or the unsaturated alkyl containing end thiazolinyl of C1～C6, more specifically, be independently selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, vinyl, allyl group, 3-methacrylic, 1-alkene butyl, 4-methyl isophthalic acid-alkene amyl group or 1-alkene amyl group; Wherein, R
1-3, R
2-3, R
3-3, R
4-3, R
5-3, R
6-3, R
7-3, R
8-3, R
9-3, R
10-3, R
11-3and R
12-3in preferably have at least two groups be selected from C1～C15 containing end thiazolinyl unsaturated alkyl, more preferably have at least two groups to be selected from the unsaturated alkyl containing end thiazolinyl of C1～C10, most preferably have at least two groups to be selected from the unsaturated alkyl containing end thiazolinyl of C1～C6, more preferably have at least two groups to be selected from vinyl, allyl group, 3-methacrylic, 1-alkene butyl, 4-methyl isophthalic acid-alkene amyl group or 1-alkene amyl group.
Antioxidant of the present invention is zinc dibutyldithiophosphate, N, N '-bis-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] one or more in hydrazine and zinc dibutyl dithiocarbamate, N more preferably, the mixture of N '-bis-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine and zinc dibutyl dithiocarbamate.
The present invention does not have particular requirement to polypropylene, well known to a person skilled in the art the polypropylene that can be used for preparing covering material.
The present invention also provides a kind of preparation method of polypropylene covering material, comprising:
1) by containing poly organic silicon sesquioxyalkane, polypropylene and the antioxidant blend of holding thiazolinyl, obtain blend;
2) by step 1) blend molding that obtains, irradiation, obtains polypropylene covering material.
According to the present invention, by containing poly organic silicon sesquioxyalkane, polypropylene and the antioxidant blend of holding thiazolinyl, obtain blend; Described antioxidant is zinc dibutyldithiophosphate, N, N '-bis-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] one or more in hydrazine and zinc dibutyl dithiocarbamate, N more preferably, the mixture of N '-bis-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine and zinc dibutyl dithiocarbamate; The present invention does not have particular requirement to polypropylene, well known to a person skilled in the art the polypropylene that can be used for preparing covering material; The described T that holds the poly organic silicon sesquioxyalkane of thiazolinyl to be preferably to there is formula (I) structure that contains
8cage modle poly organic silicon sesquioxyalkane, there is the T of formula (II) structure
10cage modle poly organic silicon sesquioxyalkane and the T with formula (III) structure
12one or more in cage modle poly organic silicon sesquioxyalkane, more preferably T
8cage modle poly organic silicon sesquioxyalkane, there is the T of formula (II) structure
10cage modle poly organic silicon sesquioxyalkane, there is the T of formula (III) structure
12cage modle poly organic silicon sesquioxyalkane or there is the T of formula (I) structure
8cage modle poly organic silicon sesquioxyalkane, there is the T of formula (II) structure
10cage modle poly organic silicon sesquioxyalkane and the T with formula (III) structure
12the mixture of cage modle poly organic silicon sesquioxyalkane; T more preferably
8cage modle poly organic silicon sesquioxyalkane, there is the T of formula (II) structure
10cage modle poly organic silicon sesquioxyalkane, there is the T of formula (III) structure
12cage modle poly organic silicon sesquioxyalkane, there is the T of formula (I) structure
8cage modle poly organic silicon sesquioxyalkane and the T with formula (II) structure
10the mixture of cage modle poly organic silicon sesquioxyalkane, there is the T of formula (I) structure
8cage modle poly organic silicon sesquioxyalkane and the T with formula (III) structure
12the mixture of cage modle poly organic silicon sesquioxyalkane, there is the T of formula (II) structure
10cage modle poly organic silicon sesquioxyalkane and the T with formula (III) structure
12the mixture of cage modle poly organic silicon sesquioxyalkane or there is the T of formula (I) structure
8cage modle poly organic silicon sesquioxyalkane, there is the T of formula (II) structure
10cage modle poly organic silicon sesquioxyalkane and the T with formula (III) structure
12the mixture of cage modle poly organic silicon sesquioxyalkane;
formula (I),
formula (II),
formula (III),
Described R
1-1, R
2-1, R
3-1, R
4-1, R
5-1, R
6-1, R
7-1, R
8-1preferably independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, more preferably independently be selected from the alkyl of C1～C6 or the unsaturated alkyl containing end thiazolinyl of C1～C10, most preferably be and be independently selected from the alkyl of C1～C4 or the unsaturated alkyl containing end thiazolinyl of C1～C6, more specifically, be independently selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, vinyl, allyl group, 3-methacrylic, 1-alkene butyl, 4-methyl isophthalic acid-alkene amyl group or 1-alkene amyl group; Wherein, described R
1-1, R
2-1, R
3-1, R
4-1, R
5-1, R
6-1, R
7-1and R
8-1in preferably have at least two groups be selected from C1～C15 containing end thiazolinyl unsaturated alkyl, more preferably have at least two groups to be selected from the unsaturated alkyl containing end thiazolinyl of C1～C10, most preferably have at least two groups to be selected from the unsaturated alkyl containing end thiazolinyl of C1～C6, more preferably have at least two groups to be selected from vinyl, allyl group, 3-methacrylic, 1-alkene butyl, 4-methyl isophthalic acid-alkene amyl group or 1-alkene amyl group; Described R
1-2, R
2-2, R
3-2, R
4-2, R
5-2, R
6-2, R
7-2, R
8-2, R
9-2, R
10-2preferably independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, more preferably independently be selected from the alkyl of C1～C6 or the unsaturated alkyl containing end thiazolinyl of C1～C10, most preferably be and be independently selected from the alkyl of C1～C4 or the unsaturated alkyl containing end thiazolinyl of C1～C6, more specifically, be independently selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, vinyl, allyl group, 3-methacrylic, 1-alkene butyl, 4-methyl isophthalic acid-alkene amyl group or 1-alkene amyl group; Wherein, R
1-2, R
2-2, R
3-2, R
4-2, R
5-2, R
6-2, R
7-2, R
8-2, R
9-2and R
10-2in preferably have at least two groups be selected from C1～C15 containing end thiazolinyl unsaturated alkyl, more preferably have at least two groups to be selected from the unsaturated alkyl containing end thiazolinyl of C1～C10, most preferably have at least two groups to be selected from the unsaturated alkyl containing end thiazolinyl of C1～C6, more preferably have at least two groups to be selected from vinyl, allyl group, 3-methacrylic, 1-alkene butyl, 4-methyl isophthalic acid-alkene amyl group or 1-alkene amyl group; Described R
1-3, R
2-3, R
3-3, R
4-3, R
5-3, R
6-3, R
7-3, R
8-3, R
9-3, R
10-3, R
11-3, R
12-3preferably independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, more preferably independently be selected from the alkyl of C1～C6 or the unsaturated alkyl containing end thiazolinyl of C1～C10, most preferably be and be independently selected from the alkyl of C1～C4 or the unsaturated alkyl containing end thiazolinyl of C1～C6, more specifically, be independently selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, vinyl, allyl group, 3-methacrylic, 1-alkene butyl, 4-methyl isophthalic acid-alkene amyl group or 1-alkene amyl group; Wherein, R
1-3, R
2-3, R
3-3, R
4-3, R
5-3, R
6-3, R
7-3, R
8-3, R
9-3, R
10-3, R
11-3and R
12-3in preferably have at least two groups be selected from C1～C15 containing end thiazolinyl unsaturated alkyl, more preferably have at least two groups to be selected from the unsaturated alkyl containing end thiazolinyl of C1～C10, most preferably have at least two groups to be selected from the unsaturated alkyl containing end thiazolinyl of C1～C6, more preferably have at least two groups to be selected from vinyl, allyl group, 3-methacrylic, 1-alkene butyl, 4-methyl isophthalic acid-alkene amyl group or 1-alkene amyl group.
Of the present invention containing holds the poly organic silicon sesquioxyalkane of thiazolinyl and described polyacrylic mass ratio to be preferably (0.3～5): 100, more preferably (0.5～5): 100, most preferably be (1～3): 100; Described antioxidant and described polyacrylic mass ratio are preferably (0.2～0.8): 1, more preferably (0.3～0.6): 1, most preferably be (0.4～0.5): 1; The present invention does not have particular requirement to the mode of blend, preferably uses high-speed mixer to mix.
In order to make blend be easy to moulding, the present invention is preferably by blend granulation, the present invention does not have particular requirement to the mode of granulation, preferably use twin screw extruder to carry out granulation, the temperature of described granulation is preferably 170～190 ℃, the particle that granulation of the present invention obtains is preferably the particle of 3～5mm, and for moisture content in the section bar that makes to obtain is less, the present invention is preferably dried to moisture content the blend of granulation lower than 0.02%.
According to the present invention, by the blend molding obtaining, irradiation, obtains polypropylene covering material; Described moulding is preferably the casting films that is prepared into 0.4～0.6mm; The irradiation dose of described cross-linking radiation is preferably 10～150kGy, and more preferably 15～100kGy, most preferably is 20～50kGy; Described source of radiation is preferably Co-60 source or rumbatron, and the atmosphere of described irradiation is preferably irradiation under vacuum or protection of inert gas.
The invention provides a kind of polypropylene covering material, by containing, hold poly organic silicon sesquioxyalkane, polypropylene and the antioxidant of thiazolinyl to make through cross-linking radiation; The present invention is by carrying out cross-linking radiation by the polypropylene that contains the poly organic silicon sesquioxyalkane of holding thiazolinyl, make the polypropylene covering material obtaining in moulding process, can make superficial makings retain completely, and the mechanical property of the polypropylene covering material obtaining is better, and then make polypropylene covering material that the present invention obtains be adapted to pass through plastic uptake to prepare polypropylene overlay film; In addition, because the present invention holds the poly organic silicon sesquioxyalkane of thiazolinyl as linking agent promotor using containing, in making that linking agent in polypropylene covering material that the present invention prepares is residual and can not using in the later stage, slowly separate out, improve the stability of polypropylene covering material.
Below in conjunction with the embodiment of the present invention, technical scheme of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
By the T with formula (I) structure of 100g polypropylene, 0.5g
8after cage modle poly organic silicon sesquioxyalkane, 0.2g zinc dibutyl dithiocarbamate and 0.2g oxidation inhibitor 1024 mix in high-speed mixer; add in twin screw extruder; at 170～190 ℃ of blending extrusions; material strip is passed through dicing machine after crossing water cooling; the blend particle that acquisition length is 3～5mm; after blend particle is dried and is less than 0.02% to moisture content; join in casting machine; being prepared into thickness is 0.5mm casting films; then casting films is placed in to Co-60 source; under nitrogen protection, the irradiation through 20kGy, obtains polypropylene covering material.
The T wherein, with formula (I) structure
8in cage modle poly organic silicon sesquioxyalkane, R
1-1for-CH
2-CH=CH
2, R
2-1for-CH
2-CH
2-CH=CH
2, R
3-1, R
4-1, R
5-1, R
6-1, R
7-1, R
8-1be-CH
3.
The polypropylene covering material that embodiment 1 is prepared carries out performance test, and result is referring to table 1, the performance test results of the polypropylene covering material that table 1 provides for the embodiment of the present invention and comparative example.
By polypropylene covering material that embodiment 1 is obtained in convection oven after 120 ℃ of processing observation period surface topography, result is referring to Fig. 1, Fig. 1 is the polypropylene covering material of the embodiment of the present invention 1 preparation surface topography after 120 ℃ of processing, as can be seen from the figure polypropylene covering material its superficial makings after 120 ℃ of processing that, prepared by the present invention retains completely.
Embodiment 2
T 100g polypropylene and 1g to formula (II) structure
10after cage modle poly organic silicon sesquioxyalkane, 0.2g zinc dibutyl dithiocarbamate, 0.2g oxidation inhibitor 1024 mix in high-speed mixer; add in twin screw extruder; at 170～190 ℃ of blending extrusions; material strip is passed through dicing machine after crossing water cooling; the blend particle that acquisition length is 3～5mm; after blend particle is dried and is less than 0.02% to moisture content; join in casting machine; being prepared into thickness is 0.5mm casting films; then casting films is placed in to Co-60 source; under nitrogen protection, the irradiation through 15kGy, obtains polypropylene covering material.
The T wherein, with formula (II) structure
10in cage modle poly organic silicon sesquioxyalkane, R
1-2for-CH
2-CH=CH
2, R
3-2for-CH
2-CH (CH
3) CH
2-CH=CH
2, R
7-2for-CH (CH
3) CH=CH
2, R
2-2, R
4-2, R
5-2, R
6-2, R
8-2, R
9-2, R
10-2be-CH
3.
The polypropylene covering material that embodiment 2 is prepared carries out performance test, and result is referring to table 1, the performance test results of the polypropylene covering material that table 1 provides for the embodiment of the present invention and comparative example.
By polypropylene covering material that embodiment 2 is obtained in convection oven after 120 ℃ of processing observation period surface topography, result is referring to Fig. 2, Fig. 2 is the polypropylene covering material of the embodiment of the present invention 2 preparation surface topography after 120 ℃ of processing, as can be seen from the figure polypropylene covering material its superficial makings after 120 ℃ of processing that, prepared by the present invention retains completely.
Embodiment 3
T 100g polypropylene and 1.5g to formula (III) structure
12after cage modle poly organic silicon sesquioxyalkane, 0.2g zinc dibutyl dithiocarbamate and 0.2g oxidation inhibitor 1024 mix in high-speed mixer; add in twin screw extruder; at 170～190 ℃ of blending extrusions; material strip is passed through dicing machine after crossing water cooling; the blend particle that acquisition length is 3～5mm; after blend particle is dried and is less than 0.02% to moisture content; join in casting machine; being prepared into thickness is 0.5mm casting films; then casting films is placed in to rumbatron; under nitrogen protection, the irradiation through 50kGy, obtains polypropylene covering material.
The T wherein, with formula (III) structure
12in cage modle poly organic silicon sesquioxyalkane, R
1-3, R
10-3for-CH=CH
2, R
3-3for-CH
2-CH
2-CH=CH
2, R
9-3for-CH (CH
3) CH=CH
2, R
2-3, R
4-3, R
5-3, R
6-3, R
7-3, R
8-3, R
11-3, R
12-3be-CH
3.
The polypropylene covering material that embodiment 3 is prepared carries out performance test, and result is referring to table 1, the performance test results of the polypropylene covering material that table 1 provides for the embodiment of the present invention and comparative example.
By polypropylene covering material that embodiment 3 is obtained in convection oven after 120 ℃ of processing observation period surface topography, result is referring to Fig. 3, Fig. 3 is the polypropylene covering material of the embodiment of the present invention 3 preparation surface topography after 120 ℃ of processing, as can be seen from the figure polypropylene covering material its superficial makings after 120 ℃ of processing that, prepared by the present invention retains completely.
Embodiment 4
T 1g to formula (I) structure
8cage modle poly organic silicon sesquioxyalkane, 1g have the T of formula (II) structure
10cage modle poly organic silicon sesquioxyalkane and 1g have the T of formula (III) structure
12cage modle poly organic silicon sesquioxyalkane mixes the composite POSS of acquisition, then by 100g polypropylene and above-mentioned composite POSS, after 0.2g zinc dibutyl dithiocarbamate and 0.2g oxidation inhibitor 1024 mix in high-speed mixer, add in twin screw extruder, at 170～190 ℃ of blending extrusions, material strip is passed through dicing machine after crossing water cooling, the blend particle that acquisition length is 3～5mm, after blend particle is dried and is less than 0.02% to moisture content, join in casting machine, being prepared into thickness is 0.5mm casting films, then casting films is placed in to Co-60 source, in vacuum environment, irradiation through 50kGy, obtain polypropylene covering material.
The T wherein, with formula (I) structure
8in cage modle poly organic silicon sesquioxyalkane, R
1-1for-CH
2-CH=CH
2, R
2-1for-CH
2-CH
2-CH=CH
2, R
3-1, R
4-1, R
5-1, R
6-1, R
7-1, R
8-1be-CH
3, there is the T of formula (II) structure
10in cage modle poly organic silicon sesquioxyalkane, R
1-2, R
10-2for-CH=CH
2, R
3-2for-CH
2-CH
2-CH=CH
2, R
9-2for-CH (CH
3) CH=CH
2, R
2-2, R
4-2, R
5-2, R
6-2, R
7-2, R
8-2be-CH
3, there is the T of formula (III) structure
12in cage modle poly organic silicon sesquioxyalkane, R
1-3, R
10-3for-CH=CH
2, R
3-3for-CH
2-CH
2-CH=CH
2, R
9-3for-CH (CH
3) CH=CH
2, R
2-3, R
4-3, R
5-3, R
6-3, R
7-3, R
8-3, R
11-3, R
12-3be-CH
3.
The polypropylene covering material that embodiment 4 is prepared carries out performance test, and result is referring to table 1, the performance test results of the polypropylene covering material that table 1 provides for the embodiment of the present invention and comparative example.
By polypropylene covering material that embodiment 4 is obtained in convection oven after 120 ℃ of processing observation period surface topography, result is referring to Fig. 4, Fig. 4 is the polypropylene covering material of the embodiment of the present invention 4 preparation surface topography after 120 ℃ of processing, as can be seen from the figure polypropylene covering material its superficial makings after 120 ℃ of processing that, prepared by the present invention retains completely.
Comparative example 1
After 100g polypropylene and 0.2g zinc dibutyl dithiocarbamate and 0.2g oxidation inhibitor are mixed in high-speed mixer; add in twin screw extruder; at 170～190 ℃ of blending extrusions; material strip is passed through dicing machine after crossing water cooling; the blend particle that to obtain length be 3～5mm, after blend particle is dried and is less than 0.02% to moisture content, joins in casting machine; being prepared into thickness is 0.5mm casting films, is polypropylene covering material.
The polypropylene covering material that comparative example 1 is prepared carries out performance test, and result is referring to table 1, the performance test results of the polypropylene covering material that table 1 provides for the embodiment of the present invention and comparative example.
By polypropylene covering material that comparative example 1 is obtained in convection oven after 120 ℃ of processing observation period surface topography, result is referring to Fig. 5, Fig. 5 is the polypropylene covering material of the comparative example of the present invention 1 preparation surface topography after 120 ℃ of processing, as can be seen from the figure, polypropylene covering material its superficial makings after 120 ℃ of processing of comparative example 1 preparation deforms.
The performance test results of the polypropylene covering material that table 1 embodiment of the present invention and comparative example provide
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a polypropylene covering material, holds poly organic silicon sesquioxyalkane, polypropylene and the antioxidant of thiazolinyl to make through cross-linking radiation by containing.
2. covering material according to claim 1, is characterized in that, described in contain hold thiazolinyl poly organic silicon sesquioxyalkane for thering is the T of formula (I) structure
8cage modle poly organic silicon sesquioxyalkane, there is the T of formula (II) structure
10cage modle poly organic silicon sesquioxyalkane and the T with formula (III) structure
12one or more in cage modle poly organic silicon sesquioxyalkane,
formula (I),
formula (II),
formula (III),
Described R
1-1, R
2-1, R
3-1, R
4-1, R
5-1, R
6-1, R
7-1, R
8-1independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, wherein, R
1-1, R
2-1, R
3-1, R
4-1, R
5-1, R
6-1, R
7-1and R
8-1in have at least two groups be selected from C1～C15 containing end thiazolinyl unsaturated alkyl;
Described R
1-2, R
2-2, R
3-2, R
4-2, R
5-2, R
6-2, R
7-2, R
8-2, R
9-2, R
10-2independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, wherein, R
1-2, R
2-2, R
3-2, R
4-2, R
5-2, R
6-2, R
7-2, R
8-2, R
9-2and R
10-2in have at least two be selected from C1～C15 containing end thiazolinyl unsaturated alkyls;
Described R
1-3, R
2-3, R
3-3, R
4-3, R
5-3, R
6-3, R
7-3, R
8-3, R
9-3, R
10-3, R
11-3, R
12-3independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, wherein, R
1-3, R
2-3, R
3-3, R
4-3, R
5-3, R
6-3, R
7-3, R
8-3, R
9-3, R
10-3, R
11-3and R
12-3in have at least two be selected from C1～C15 containing end thiazolinyl unsaturated alkyls.
3. covering material according to claim 1, is characterized in that, described in contain that to hold the poly organic silicon sesquioxyalkane of thiazolinyl and described polyacrylic mass ratio be (0.3～5): 100.
4. covering material according to claim 1, it is characterized in that, described antioxidant is zinc dibutyldithiophosphate, N, one or more in N '-bis-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine and zinc dibutyl dithiocarbamate.
5. covering material according to claim 1, is characterized in that, described antioxidant and described polyacrylic mass ratio are (0.2～0.8): 1.
6. covering material according to claim 1, is characterized in that, the radiation dose of described cross-linking radiation is 10～150kGy.
7. a preparation method for polypropylene covering material, comprising:
1) by containing poly organic silicon sesquioxyalkane, polypropylene and the antioxidant blend of holding thiazolinyl, obtain blend;
2) by step 1) blend molding that obtains, irradiation, obtains polypropylene covering material.
8. preparation method according to claim 7, is characterized in that, described in contain that to hold the poly organic silicon sesquioxyalkane of thiazolinyl and described polyacrylic mass ratio be (0.3～5): 100.
9. preparation method according to claim 7, is characterized in that, described in contain hold thiazolinyl poly organic silicon sesquioxyalkane for thering is the T of formula (I) structure
8cage modle poly organic silicon sesquioxyalkane, there is the T of formula (II) structure
10cage modle poly organic silicon sesquioxyalkane and the T with formula (III) structure
12one or more in cage modle poly organic silicon sesquioxyalkane,
formula (I),
formula (II),
formula (III),
Described R
1-1, R
2-1, R
3-1, R
4-1, R
5-1, R
6-1, R
7-1, R
8-1independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, wherein, R
1-1, R
2-1, R
3-1, R
4-1, R
5-1, R
6-1, R
7-1and R
8-1in have at least two groups be selected from C1～C15 containing end thiazolinyl unsaturated alkyl;
Described R
1-2, R
2-2, R
3-2, R
4-2, R
5-2, R
6-2, R
7-2, R
8-2, R
9-2, R
10-2independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, wherein, R
1-2, R
2-2, R
3-2, R
4-2, R
5-2, R
6-2, R
7-2, R
8-2, R
9-2and R
10-2in have at least two be selected from C1～C15 containing end thiazolinyl unsaturated alkyls;
Described R
1-3, R
2-3, R
3-3, R
4-3, R
5-3, R
6-3, R
7-3, R
8-3, R
9-3, R
10-3, R
11-3, R
12-3independently be selected from the alkyl of C1～C10 or the unsaturated alkyl containing end thiazolinyl of C1～C15, wherein, R
1-3, R
2-3, R
3-3, R
4-3, R
5-3, R
6-3, R
7-3, R
8-3, R
9-3, R
10-3, R
11-3and R
12-3in have at least two be selected from C1～C15 containing end thiazolinyl unsaturated alkyls.
10. preparation method according to claim 7, is characterized in that, the radiation dose of described cross-linking radiation is 10～150kGy.
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| WO2020010514A1 (en) * | 2018-07-10 | 2020-01-16 | 深圳市摩码科技有限公司 | Crosslinked film and preparation method therefor |
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| CN110372962A (en) * | 2019-08-12 | 2019-10-25 | 福建拓烯新材料科技有限公司 | A kind of cross-linking type POSS/PP composite diaphragm, preparation method and application |
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Application publication date: 20141210 |