CN106189244A - A kind of environmentally-friendly transparent type POSS modified calcium zinc stabilizer and preparation method thereof - Google Patents
A kind of environmentally-friendly transparent type POSS modified calcium zinc stabilizer and preparation method thereof Download PDFInfo
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- CN106189244A CN106189244A CN201610693296.9A CN201610693296A CN106189244A CN 106189244 A CN106189244 A CN 106189244A CN 201610693296 A CN201610693296 A CN 201610693296A CN 106189244 A CN106189244 A CN 106189244A
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Abstract
Open a kind of environmentally-friendly transparent type POSS modified calcium zinc stabilizer of the present invention and preparation method thereof, is prepared from by the raw material including following weight portion: fatty acid calcium 20 ~ 30 parts；Aromatic acid 15 ~ 25 parts；Auxiliary stabilizer 4 ~ 6 parts；DMF 80 ~ 100 parts；POSS 5 ~ 10 parts.The POSS modified calcium zinc stabilizer of the present invention can improve the heat resistance of PVC product further.In this system, take full advantage of unique organo-silicon compound molecular structure of POSS and inorganic silica skeleton, it is blended with calcium zinc stabilizer, it is possible to significantly improve its heat stability, processing characteristics and fire resistance.Preparation method of the present invention has efficiently, the feature of asepsis environment-protecting, is a kind of synthesis preparation method with universality.
Description
Technical field
The present invention relates to modified chemical stabilizer technical field, particularly relate to a kind of environmentally-friendly transparent type POSS modified calcium zinc steady
Determine agent and preparation method thereof.
Background technology
Cagelike silsesquioxane (POSS) is the organosilicon compound of molecule size special construction between 1～3nm
Thing.Organic and the inorganic feature of POSS and derivant set thereof, has the strongest structure designability and " cutting " property simultaneously.
The inorganic silica scaffold core of its molecule provides good thermostability for material, and being positioned at the silicon atom on hexahedron angle can be by changing
Learn reaction and introduce multiple organic group with the compatibility improved and between polymeric matrix.
Polrvinyl chloride (PVC) plastics have excellence mechanical property, can be combined well with common fillers, heatproof up to
105 DEG C, the oxygen index (OI) of pure PVC is up to 41%.PVC also has the electrical insulation properties of excellence, thus at wires and cables industry, special
It not in terms of low tension wire cable, occupy great advantage.But common PVC CABLE MATERIALS contains heavy metal element lead, cadmium etc. to be had
Pest matter, thus become its key factor used in the occasion such as electrical equipment, infrastructure of restriction.At present with inside and outside to environmental protection
The developed countries such as the demand of type CABLE MATERIALS increases rapidly, American-European make the heavy metal elements such as lead, cadmium, hydrargyrum and many bromines connection the most in succession
The benzene class harmful substance protective standard to environment, such as Britain--European standard BSEN.71, ENll22, Environmental Protection Agency USA marks
Quasi-US EPA3050B etc., soft pvc CABLE MATERIALS unleaded nontoxic be trend of the times, environment-friendly type PVC CABLE MATERIALS has become current cable
Material research and development and the important topic produced.
Owing to PVC is the white powder of impalpable structure, the degree of branching is less, the poor stability to light and heat, when 140 DEG C
Begin to decompose, but the processing temperature of PVC is at 170-200 DEG C, therefore, during actual application, stabilizer must be added in PVC
Improve its stability to light and heat, prevent or slow down its thermal degradation during processing or use.
Heat stabilizer the more commonly used in PVC industry has lead salt, organic tin, metal soap, terres rares and calcium zinc class
Deng stabilizer.Lead salt stabilizer was once the heat stabilizer that PVC is the most frequently used, cheap, Heat stability is good, but its toxicity is big,
Easily to environment.Organic tin and metal soap are the most more common non-toxic stabilizers.Organic tin price is high,
Considering Financial cost benefit, its application is restricted.Metal soap is used alone weak effect, generally by main and auxiliary metallic soap and auxiliary
Co-stabilizer compounds, it is thus achieved that composite thermal stabilizer.It is poisonous stable that calcium zinc type thermal stabilizing agent not only can replace lead cadmium salt class
Agent, and there is goodish heat stability, light stability and the transparency and tinting strength, tinting power, it is a kind of good non-toxic stabilizer.
The main white powdery of calcium zinc stabilizer outward appearance, lamellar, paste.The calcium zinc stabilizer of powdery is as application the most
The most nontoxic PVC stabilizer uses, and is usually used in packaging for foodstuff, medical apparatus and instruments, wire cable material etc..The most domestic occurred
Can be used for the PVC calcium zinc stabilizer of hard tubing.The heat stability of powdered calcium zinc stabilizer is not so good as lead salt, self has certain
Lubricity, the features such as the transparency is poor, easy bloom.In order to improve its stability and the transparency, usually add hindered phenol, polyhydric alcohol,
Phosphite ester improves with antioxidant such as beta-diketons.With the polyvinyl chloride resin course of processing has good dispersibility, the compatibility, processing
Mobility, wide adaptability, product surface fineness is excellent；Good heat stability, initial stage form and aspect are little, without precipitation phenomenon；Without a huge sum of money
Belong to and other toxic components, without sulfation；The Congo red testing time is long, has excellent electrical insulating property, free from admixture, has height
Effect weatherability；Applied widely, practical, consumption is few, has multifunctionality；In white article, whiteness is compared with its similar product
Product are more preferably.
Metal soap stabilizer is the general name of higher fatty acid metal salt, and it falls within the big class of in calcium zinc stabilizer,
Kind is a lot.In metallic soap as calcium carbide process PVC heat stabilizer, Metal Substrate uses most usually cadmium, barium, zinc, calcium, magnesium
In metal, alkaline-earth metal etc., fatty acid-based conventional be the unsaturated lipids such as stearic acid (HSt), C8-16 satisfied fatty acid, oleic acid
Fat acid, wherein HSt base is the most commonly used.Metal soap can also be that two or more organic metal salt is added
Some is chosen for the complex that auxiliary agent is formed.Metal soap has lubricity, and the transparency is also good compared with lead salt, but
Heat stability is not so good as lead salt and organotin.Metallic soap is the most nontoxic in addition to Cd, Pb；In addition to Pb, Ca the most transparent；Its stablizing effect is successively
For: Zn salt > Cd salt > Pb salt > Ca salt > Ba salt.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of environmentally-friendly transparent type POSS modified calcium zinc
Stabilizer and preparation method thereof, it is intended to solve existing heat stabilizer and there is part heavy metal, not environmental protection, expensive, and
The problem that thermostable effect is the best.
Technical scheme is as follows:
A kind of environmentally-friendly transparent type POSS modified calcium zinc stabilizer, wherein, is prepared from by the raw material including following weight portion:
Fatty acid calcium 20 ~ 30 parts；
15 ~ 25 parts of aromatic acid zinc；
Auxiliary stabilizer 4 ~ 6 parts；
DMF 80 ~ 100 parts；
POSS 5 ~ 10 parts.
Described environmentally-friendly transparent type POSS modified calcium zinc stabilizer, wherein, by include following weight portion raw material prepare and
Become:
Fatty acid calcium 25 parts；
20 parts of aromatic acid zinc；
Auxiliary stabilizer 5 parts；
DMF 90 parts；
POSS 8 parts.
Described environmentally-friendly transparent type POSS modified calcium zinc stabilizer, wherein, described fatty acid calcium is calcium stearate.
Described environmentally-friendly transparent type POSS modified calcium zinc stabilizer, wherein, described aromatic acid zinc is zinc stearate.
Described environmentally-friendly transparent type POSS modified calcium zinc stabilizer, wherein, described auxiliary stabilizer is phosphite ester.
Described environmentally-friendly transparent type POSS modified calcium zinc stabilizer, wherein, described phosphite ester is triphenyl phosphite, Asia
One or more in tridecyl phosphate, trisnonyl phenyl phosphite, tricresyl phosphite monooctyl ester.
The preparation method of arbitrary a kind of described environmentally-friendly transparent type POSS modified calcium zinc stabilizer, wherein, including step
Rapid:
Add raw materials in reaction vessel by said ratio, at 130 ~ 150 DEG C, uniformly mix 1.8 ~ 2.2h, then will
Mixed solution filters, evacuation, and dries at 70 ~ 90 DEG C, it is thus achieved that POSS modified calcium zinc stabilizer.
The preparation method of described environmentally-friendly transparent type POSS modified calcium zinc stabilizer, wherein, including step:
Add raw materials in reaction vessel by said ratio, at 140 DEG C, uniformly mix 2h, then by mixed solution mistake
Filter, evacuation, and dry at 80 DEG C, it is thus achieved that POSS modified calcium zinc stabilizer.
Beneficial effect: owing to POSS has the organo-silicon compound molecular structure of uniqueness and inorganic silica skeleton so that it is tool
There are good hardness and heat stability.Calcium zinc stabilizer is modified by the present invention by POSS, can improve this calcium zinc further
The heat stability of stabilizer.And the modified calcium zinc stabilizer high-efficiency environment friendly of gained is nontoxic, is with a wide range of applications.
Detailed description of the invention
The present invention provides a kind of environmentally-friendly transparent type POSS modified calcium zinc stabilizer and preparation method thereof, for making the mesh of the present invention
, technical scheme and effect clearer, clear and definite, the present invention is described in more detail below.Should be appreciated that described herein
Specific embodiment only in order to explain the present invention, be not intended to limit the present invention.
The present invention provides a kind of environmentally-friendly transparent type POSS modified calcium zinc stabilizer, wherein, by including the former of following weight portion
Material is prepared from:
Fatty acid calcium 20 ~ 30 parts；
15 ~ 25 parts of aromatic acid zinc；
Auxiliary stabilizer 4 ~ 6 parts；
Dimethylformamide (DMF) 80 ~ 100 parts；
POSS 5 ~ 10 parts.
Owing to POSS has the organo-silicon compound molecular structure of uniqueness and inorganic silica skeleton so that it is have good hard
Degree and heat stability.Calcium zinc stabilizer is modified by the present invention by POSS, can improve the heat of this calcium zinc stabilizer further
Stability.And the modified calcium zinc stabilizer high-efficiency environment friendly of gained is nontoxic, is with a wide range of applications.
Preferably, one environmentally-friendly transparent type POSS modified calcium zinc stabilizer of the present invention, wherein, by including following weight portion
Raw material is prepared from:
Fatty acid calcium 25 parts；
20 parts of aromatic acid zinc；
Auxiliary stabilizer 5 parts；
DMF 90 parts；
POSS 8 parts.
Under above-mentioned optimization formula, it is thus achieved that POSS modified calcium zinc stabilizer there is more preferable thermostable effect and transparent
Property.
Preferably, fatty acid calcium of the present invention can be but be not limited to calcium stearate.
Preferably, aromatic acid zinc of the present invention can be but be not limited to zinc stearate.
Preferably, auxiliary stabilizer of the present invention can be but be not limited to phosphite ester.Wherein, described phosphite ester can
Think one or more in triphenyl phosphite, tridecyl phosphite, trisnonyl phenyl phosphite, tricresyl phosphite monooctyl ester.
POSS of the present invention is cage modle polysilsesquioxane, and its structural formula is as follows:
The present invention is stable using fatty acid calcium (such as calcium stearate), aromatic acid zinc (such as zinc stearate) and auxiliary stabilizer as calcium zinc
Agent, is blended it with POSS, to obtain POSS modified calcium zinc stabilizer in DMF solution.The present invention uses POSS as modification
Agent, is owing to POSS has the organo-silicon compound molecular structure of uniqueness and inorganic silica skeleton, it is possible to improve calcium zinc further
The heat stability of stabilizer, processing characteristics and fire resistance.
POSS modified calcium zinc stabilizer of the present invention is a kind of high-performance organic-inorganic hybrid material, is inorganic one-tenth with POSS
Point, inorganic phase is with organic alternate by strong chemical bonds, and the reunion and the two-phase interface adhesion that there is not inorganic particulate are weak
Problem, it is easy to by copolymerization, mode and the polymeric matrix such as be grafted or be blended and carry out compound preparation.
Compared with existing calcium zinc stabilizer, the POSS modified calcium zinc stabilizer of gained of the present invention has a following excellent properties:
(1), temperature is used to increase；
(2), mechanical property improves；
(3), processing characteristics improves；
(4), there is significant delayed combustion characteristic；
(5), can be with multifunction, using POSS as END CAPPED GROUP or crosslinking curing center, it is possible to obtain meet changing of different needs
Property calcium zinc stabilizer.
Based on above-mentioned environmentally-friendly transparent type POSS modified calcium zinc stabilizer, the present invention also provides for a kind of arbitrary described saturating
The preparation method of bright environment-friendly type POSS modified calcium zinc stabilizer, it includes step:
Add raw materials in reaction vessel by said ratio, under 130 ~ 150 DEG C (such as 140 DEG C), uniformly mix 1.8 ~
2.2h(such as 2h), then mixed solution is filtered, evacuation, and dry under 70 ~ 90 DEG C (such as 80 DEG C), it is thus achieved that POSS modified calcium
Zinc stabilizer.
Below by embodiment, the present invention is described in detail.
Embodiment 1
(1), dispensing
A kind of environmentally-friendly transparent type POSS modified calcium zinc stabilizer, is prepared from by the raw material including following weight portion:
Fatty acid calcium 25 parts；
20 parts of aromatic acid zinc；
Auxiliary stabilizer 5 parts；
DMF 90 parts；
POSS 8 parts.
(2), the preparation of environmentally-friendly transparent type POSS modified calcium zinc stabilizer
Add raw materials in reaction vessel by said ratio, at 140 DEG C, uniformly mix 2h, then by mixed solution mistake
Filter, evacuation, and dry at 80 DEG C, it is thus achieved that POSS modified calcium zinc stabilizer.
(3), application and performance test
By weight, according to following formula, the POSS modified calcium zinc stabilizer of PVC, plasticizer, filler and preparation is mixed:
PVC 100 parts；
Plasticizer 50 parts；
Filler 50 parts；
POSS modified calcium zinc stabilizer 3.6 parts.
Take the PVC of weight portion, plasticizer, filler formula material mix.It is subsequently adding POSS modified calcium zinc stable
Agent mixes, and mixes 3min, then in 180 DEG C of mixing 5min in two-roll mill, pull into thickness 1.0mm in homogenizer
Print, print tests in the steps below:
First, produce one group of print is put in TZ5043 type ageing oven carry out the heat stability testing at 180 DEG C.Often
A print is taken out, relatively each print color situation of change every 5min.The experimental result of " print thermostability " is shown in Table 1.
Table 1, print thermostability test result table
| Time/min | 5 | 10 | 15 | 20 | 25 | 30 | 35 | 40 | 45 | 50 |
| Color changes | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Pale yellow | Shallow palm fibre |
Table 1 result shows, color required time that changes is longer, and the thermal stability of product is preferable.
Embodiment 2
(1), dispensing
A kind of environmentally-friendly transparent type POSS modified calcium zinc stabilizer, is prepared from by the raw material including following weight portion:
Fatty acid calcium 22 parts；
18 parts of aromatic acid zinc；
Auxiliary stabilizer 5 parts；
DMF 85 parts；
POSS 6 parts.
(2), the preparation of environmentally-friendly transparent type POSS modified calcium zinc stabilizer
Add raw materials in reaction vessel by said ratio, at 130 DEG C, uniformly mix 1.8h, then by mixed solution
Filter, evacuation, and dry at 70 DEG C, it is thus achieved that POSS modified calcium zinc stabilizer.
(3), application and performance test
By weight, according to following formula, the POSS modified calcium zinc stabilizer of PVC, plasticizer, filler and preparation is mixed:
PVC 100 parts；
Plasticizer 50 parts；
Filler 50 parts；
POSS modified calcium zinc stabilizer 3.6 parts.
Take the PVC of weight portion, plasticizer, filler formula material mix.It is subsequently adding POSS modified calcium zinc stable
Agent mixes, and mixes 3min, then in 180 DEG C of mixing 5min in two-roll mill, pull into thickness 1.0mm in homogenizer
Print, print tests in the steps below:
First, produce one group of print is put in TZ5043 type ageing oven carry out the heat stability testing at 180 DEG C.Often
A print is taken out, relatively each print color situation of change every 5min.The experimental result of " print thermostability " is shown in Table 2.
Table 2 print thermostability test result table
| Time/min | 5 | 10 | 15 | 20 | 25 | 30 | 35 | 40 | 45 | 50 |
| Color changes | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Shallow palm fibre | Shallow palm fibre |
Table 2 result shows, color required time that changes is longer, and the thermal stability of product is preferable.
Embodiment 3
(1), dispensing
A kind of environmentally-friendly transparent type POSS modified calcium zinc stabilizer, is prepared from by the raw material including following weight portion:
Fatty acid calcium 30 parts；
25 parts of aromatic acid zinc；
Auxiliary stabilizer 6 parts；
DMF 100 parts；
POSS 10 parts.
(2), the preparation of environmentally-friendly transparent type POSS modified calcium zinc stabilizer
Add raw materials in reaction vessel by said ratio, at 150 DEG C, uniformly mix 2.2h, then by mixed solution
Filter, evacuation, and dry at 90 DEG C, it is thus achieved that POSS modified calcium zinc stabilizer.
(3), application and performance test
By weight, according to following formula, the POSS modified calcium zinc stabilizer of PVC, plasticizer, filler and preparation is mixed:
PVC 100 parts；
Plasticizer 50 parts；
Filler 50 parts；
POSS modified calcium zinc stabilizer 3.6 parts.
Take the PVC of weight portion, plasticizer, filler formula material mix.It is subsequently adding POSS modified calcium zinc stable
Agent mixes, and mixes 3min, then in 180 DEG C of mixing 5min in two-roll mill, pull into thickness 1.0mm in homogenizer
Print, print tests in the steps below:
First, produce one group of print is put in TZ5043 type ageing oven carry out the heat stability testing at 180 DEG C.Often
A print is taken out, relatively each print color situation of change every 5min.The experimental result of " print thermostability " is shown in Table 3.
Table 3, print thermostability test result table
| Time/min | 5 | 10 | 15 | 20 | 25 | 30 | 35 | 40 | 45 | 50 |
| Color changes | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Pale yellow |
Table 3 result shows, color required time that changes is longer, and the thermal stability of product is preferable.
Embodiment 4
(1), dispensing
A kind of environmentally-friendly transparent type POSS modified calcium zinc stabilizer, is prepared from by the raw material including following weight portion:
Fatty acid calcium 28 parts；
22 parts of aromatic acid zinc；
Auxiliary stabilizer 5 parts；
DMF 95 parts；
POSS 9 parts.
(2), the preparation of environmentally-friendly transparent type POSS modified calcium zinc stabilizer
Add raw materials in reaction vessel by said ratio, at 140 DEG C, uniformly mix 2h, then by mixed solution mistake
Filter, evacuation, and dry at 80 DEG C, it is thus achieved that POSS modified calcium zinc stabilizer.
(3), application and performance test
By weight, according to following formula, the POSS modified calcium zinc stabilizer of PVC, plasticizer, filler and preparation is mixed:
PVC 100 parts；
Plasticizer 50 parts；
Filler 50 parts；
POSS modified calcium zinc stabilizer 3.6 parts.
Take the PVC of weight portion, plasticizer, filler formula material mix.It is subsequently adding POSS modified calcium zinc stable
Agent mixes, and mixes 3min, then in 180 DEG C of mixing 5min in two-roll mill, pull into thickness 1.0mm in homogenizer
Print, print tests in the steps below:
First, produce one group of print is put in TZ5043 type ageing oven carry out the heat stability testing at 180 DEG C.Often
A print is taken out, relatively each print color situation of change every 5min.The experimental result of " print thermostability " is shown in Table 4.
Table 4, print thermostability test result table
| Time/min | 5 | 10 | 15 | 20 | 25 | 30 | 35 | 40 | 45 | 50 |
| Color changes | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Pale yellow |
Table 4 result shows, color required time that changes is longer, and the thermal stability of product is preferable.
Embodiment 5
(1), dispensing
A kind of environmentally-friendly transparent type POSS modified calcium zinc stabilizer, is prepared from by the raw material including following weight portion:
Fatty acid calcium 20 parts；
15 parts of aromatic acid zinc；
Auxiliary stabilizer 4 parts；
DMF 80 parts；
POSS 5 parts.
(2), the preparation of environmentally-friendly transparent type POSS modified calcium zinc stabilizer
Add raw materials in reaction vessel by said ratio, at 140 DEG C, uniformly mix 2h, then by mixed solution mistake
Filter, evacuation, and dry at 80 DEG C, it is thus achieved that POSS modified calcium zinc stabilizer.
(3), application and performance test
By weight, according to following formula, the POSS modified calcium zinc stabilizer of PVC, plasticizer, filler and preparation is mixed:
PVC 100 parts；
Plasticizer 50 parts；
Filler 50 parts；
POSS modified calcium zinc stabilizer 3.6 parts.
Take the PVC of weight portion, plasticizer, filler formula material mix.It is subsequently adding POSS modified calcium zinc stable
Agent mixes, and mixes 3min, then in 180 DEG C of mixing 5min in two-roll mill, pull into thickness 1.0mm in homogenizer
Print, print tests in the steps below:
First, produce one group of print is put in TZ5043 type ageing oven carry out the heat stability testing at 180 DEG C.Often
A print is taken out, relatively each print color situation of change every 5min.The experimental result of " print thermostability " is shown in Table 5.
Table 5, print thermostability test result table
| Time/min | 5 | 10 | 15 | 20 | 25 | 30 | 35 | 40 | 45 | 50 |
| Color changes | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless | Colourless |
Table 5 result shows, color required time that changes is longer, and the thermal stability of product is preferable.
Comparative example one
By weight, according to following formula by PVC, plasticizer, filler mixing:
PVC 100 parts；
Plasticizer 50 parts；
Filler 50 parts.
Take the PVC of weight portion, plasticizer, filler formula material mix.3min is mixed in homogenizer, and
After in 180 DEG C of mixing 5min in two-roll mill, pull into the print of thickness 1.0mm, produce print, carry out reality in the steps below
Test:
First, produce one group of print is put in TZ5043 type ageing oven carry out the heat stability testing at 180 DEG C.Often
A print is taken out, relatively each print color situation of change every 5min.The experimental result of " print thermostability " is shown in Table 6.
Table 6, print thermostability test result table
| Time/min | 5 | 10 | 15 | 20 | 25 | 30 | 35 | 40 | 45 | 50 |
| Color changes | Colourless | Pale yellow | Reddish brown | Black | Black | Black | Black | Black | Black | Black |
Table 6 result shows, color required time that changes is shorter, and the heat resistance of this explanation PVC material itself is poor.
Comparative example two
By weight, according to following formula, PVC, plasticizer, filler and composite calcium zinc stabilizing agent are mixed:
PVC 100 parts；
Plasticizer 50 parts；
Filler 50 parts；
Composite calcium zinc stabilizing agent 3.6 parts.
Take the PVC of weight portion, plasticizer, filler formula material mix.It is subsequently adding composite calcium zinc stabilizing agent,
Homogenizer mixes 3min, then in 180 DEG C of mixing 5min in two-roll mill, pulls into the print of thickness 1.0mm,
Produce print, test in the steps below:
First, produce one group of print is put in TZ5043 type ageing oven carry out the heat stability testing at 180 DEG C.Often
A print is taken out, relatively each print color situation of change every 5min.The experimental result of " print thermostability " is shown in Table 7.
Table 7, print thermostability test result table
| Time/min | 5 | 10 | 15 | 20 | 25 | 30 | 35 | 40 | 45 | 50 |
| Color changes | Colourless | Colourless | Colourless | Colourless | Colourless | Pale yellow | Shallow palm fibre | Reddish brown | Black | Black |
Table 7 result shows, in the PVC that with the addition of a certain amount of composite calcium zinc stabilizing agent, the resistance to thermal endurance of heat stability relatively contrasts
Example one has significantly prolongation.But compared with above-described embodiment, then there is bigger gap its persistent period.This explanation POSS changes
Property calcium zinc stabilizer can improve the heat stability of goods further, and modified effect is obvious.
The heat resistance test result at 180 DEG C according to above-described embodiment and comparative example, it can be seen that the present invention's
POSS modified calcium zinc stabilizer can improve the heat resistance of PVC product further.In this system, take full advantage of POSS's
Unique organo-silicon compound molecular structure and inorganic silica skeleton, be blended it with calcium zinc stabilizer, it is possible to significantly improve
Its heat stability, processing characteristics and fire resistance.This method has efficiently, the feature of asepsis environment-protecting, and it is pervasive to be that one has
The synthesis preparation method of property.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved according to the above description or to convert, all these modifications and variations all should belong to the guarantor of claims of the present invention
Protect scope.
Claims (8)
1. an environmentally-friendly transparent type POSS modified calcium zinc stabilizer, it is characterised in that prepared by the raw material including following weight portion
Form:
Fatty acid calcium 20 ~ 30 parts；
15 ~ 25 parts of aromatic acid zinc；
Auxiliary stabilizer 4 ~ 6 parts；
DMF 80 ~ 100 parts；
POSS 5 ~ 10 parts.
Environmentally-friendly transparent type POSS modified calcium zinc stabilizer the most according to claim 1, it is characterised in that following heavy by including
The raw material of amount part is prepared from:
Fatty acid calcium 25 parts；
20 parts of aromatic acid zinc；
Auxiliary stabilizer 5 parts；
DMF 90 parts；
POSS 8 parts.
Environmentally-friendly transparent type POSS modified calcium zinc stabilizer the most according to claim 1, it is characterised in that described fatty acid calcium
For calcium stearate.
Environmentally-friendly transparent type POSS modified calcium zinc stabilizer the most according to claim 1, it is characterised in that described aromatic acid zinc
For zinc stearate.
Environmentally-friendly transparent type POSS modified calcium zinc stabilizer the most according to claim 1, it is characterised in that described auxiliary is stable
Agent is phosphite ester.
Environmentally-friendly transparent type POSS modified calcium zinc stabilizer the most according to claim 5, it is characterised in that described phosphite ester
For one or more in triphenyl phosphite, tridecyl phosphite, trisnonyl phenyl phosphite, tricresyl phosphite monooctyl ester.
7. a preparation method for the environmentally-friendly transparent type POSS modified calcium zinc stabilizer as described in claim 1 ~ 6 is arbitrary, it is special
Levy and be, including step:
Add raw materials in reaction vessel by said ratio, at 130 ~ 150 DEG C, uniformly mix 1.8 ~ 2.2h, then will
Mixed solution filters, evacuation, and dries at 70 ~ 90 DEG C, it is thus achieved that POSS modified calcium zinc stabilizer.
The preparation method of environmentally-friendly transparent type POSS modified calcium zinc stabilizer the most according to claim 7, it is characterised in that bag
Include step:
Add raw materials in reaction vessel by said ratio, at 140 DEG C, uniformly mix 2h, then by mixed solution mistake
Filter, evacuation, and dry at 80 DEG C, it is thus achieved that POSS modified calcium zinc stabilizer.
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