CN108485076A - A kind of polyolefin and preparation method thereof of the novel silane coupler modified calcium carbonate containing hindered phenol - Google Patents
A kind of polyolefin and preparation method thereof of the novel silane coupler modified calcium carbonate containing hindered phenol Download PDFInfo
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- CN108485076A CN108485076A CN201810320418.9A CN201810320418A CN108485076A CN 108485076 A CN108485076 A CN 108485076A CN 201810320418 A CN201810320418 A CN 201810320418A CN 108485076 A CN108485076 A CN 108485076A
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The polyolefin of the invention discloses a kind of novel silane coupler modified calcium carbonate containing hindered phenol, it is characterised in that：The novel silane coupler of 0.1 1 parts of hindered phenol structure is added into the calcium carbonate of 30 40 mass parts, 60 DEG C of 80 DEG C of high-speed stirreds 20 30 minutes add the polyolefin to 100 mass parts, continue stirring 30 minutes, squeeze out on the twin screw extruder to get.
Description
Technical field
The present invention relates to a kind of improved polyalkenes and preparation method thereof, and in particular to a kind of novel silane containing hindered phenol is even
Join the polyolefin and preparation method thereof of agent modified calcium carbonate.
Background technology
Polyolefin is the high-molecular compound that alkene passes through that sudden reaction is formed.This kind of organic polymer is usually by many phases
With or different simple olefins be polymerized (such as polypropylene, polyethylene), the strand of molecular polyolefin is shown as significantly
Nonpolar phenomenon.Calcium carbonate by feat of the features such as cheap, non-toxic and tasteless, whiteness is high, hardness is good in rubber and plastics-production
It is widely used as filler use in the process.But since calcium carbonate is polar molecule, dispersion can be easily caused when adding pearl filler
Uneven or accumulation phenomena, so as to cause different interface is generated between filler and polymer, this defect easy tos produce stress collection
Middle phenomenon, so that the mechanical mechanics property of polyolefin declines.
Silane coupling agent is a kind of bifunctional compound of hybrid inorganic-organic, and due to this unique property, it can
Build conjunction not only chemistry can occur with organic substance, but also can interact with inorganic substances, by organic substance with it is inorganic
Substance firmly links together, and plays the role of chemical bridge.Silane coupling agent is improving between inorganic matter and organic matter
Interface interaction can improve the performances such as the crushing resistance, heat-resisting quantity, wearability of composite material.It is inorganic to fill out in polymer industry
The use of material can reduce cost, increase polymer properties.Common inorganic filler calcium carbonate, glass fibre etc. directly with it is poly-
It closes object mixing and can exist and disperse uneven, bonding interface is bad and filler agglomeration.Using silane coupling agent to inorganic filler
It is modified, the hydrophily of filler can be improved so that filler and the direct bonding interface of polymeric matrix are even closer.
Meanwhile in process, oxidation scission may occur for the chain molecule of polyolefin, it is equally possible to lead to material property
Deterioration, the oxidation occurred during subsequent use may cause polyolefine material performance to continue to reduce, influence further
It uses.During processing, storage, use, physics, chemical property and mechanical property are gradually deteriorated polyolefin.Polyolefin
It is particularly sensitive to oxidative degradation, therefore the oxidation during the process of polyolefin, use is prevented, to many materials such as rubber
It is very important for the products such as glue, plastics, fiber.It is to improve that polyolefin properties are most effective and most convenient that antioxidant, which is added,
Method.Hinered phenols antioxidant difficulty volatilization, it is non-discolouring, pollution-free, less toxic or nontoxic, wherein single phenol class be current volume of production and marketing most
Big high-efficiency anti-oxidant, this kind antioxidant there is also it is easy hydrolysis, it is volatile, easily be extracted the shortcomings of.
During doing filler using calcium carbonate and preparing polyolefin, need first to change calcium carbonate using silane coupling agent etc.
Property agent is modified, to improve the compatibility of calcium carbonate and polyolefin.It also needs to that antioxidant is added, improves molecular polyolefin chain and exist
Oxidation scission phenomenon during processing, use.But in polyolefin be added inorganic filler when, antioxidant, inorganic filler,
Polymeric matrix constitutes heterogeneous system, and the scattering problem of antioxidant and inorganic filler is relatively difficult to resolve certainly, influences polymer performance.Together
When, in polyolefin process, it usually needs be first modified using various modifying agent to inorganic filler, then in process
Addition antioxidant prevents the oxidation during the processing of polymer, use, and therefore, filler modified and addition antioxidant is independent
Process, antioxidant are difficult to be uniformly mixed, and often the oxidation scission of the polyolefin on filler periphery is the most serious with inorganic filler, because
This addition antioxidant can not preferably inhibit the polyene molecular chain rupture on filler periphery sometimes.
Invention content
The technical problem to be solved by the present invention is to：A kind of novel silane coupler modified calcium carbonate containing hindered phenol is provided
Polyolefin and preparation method thereof, it is of the existing technology to solve the problems, such as.
The technical scheme is that：A kind of polyolefin of the novel silane coupler modified calcium carbonate containing hindered phenol,
It is characterized in that：The novel silane coupler of the hindered phenol structure of 0.1-1 parts of addition into the calcium carbonate of 30-40 mass parts, 60 DEG C-
80 DEG C of high-speed stirreds 20-30 minutes, add the polyolefin to 100 mass parts, continue stirring 30 minutes, in double screw extruder
It is upper extrusion to get.
The polyolefin is atactic copolymerized polypropene, polyethylene or polystyrene.
A kind of polyolefin of the novel silane coupler modified calcium carbonate containing hindered phenol, it is characterised in that：It is described
Double screw extruder temperature：One 190 DEG C of area, two 200 DEG C of areas, three 210 DEG C of areas, four 220 DEG C of areas, five 230 DEG C of areas, head 225
℃；It is an area 55MPa, two area 50MPa, 3rd area that pellet, which will be squeezed out, in being molded obtained standard sample, injection pressure on injection molding machine
45MPa, four area 40MPa.
A kind of polyolefin of the novel silane coupler modified calcium carbonate containing hindered phenol, it is characterised in that：It is described
The novel silane coupler structural formula containing hindered phenol be：
, wherein R1For methyl, ethyl or propyl, R2For methyl, ethyl, propyl or cyclohexyl, n 1-4.
The preparation method of the novel silane coupler containing hindered phenol：In N2Under protection, 2,6- di-t-butyl -4-
After (chloromethyl) phenol, dimethyl sulfoxide and the silane coupling agent containing tertiary amine group react 8-48h at 80-100 DEG C, washing,
Vacuum drying obtains the novel antioxygen silane coupling agent containing hindered phenol structure.
Beneficial effects of the present invention：Defect in view of the prior art invents a kind of novel antioxygen silicon containing hindered phenol structure
Alkane coupling agent, this coupling agent is containing there are three functional areas：(1) hindered phenol antioxygen region can play antioxidant effect；(2) quaternary ammonium
Salt region, quaternary ammonium salt can significantly reduce the surface energy of inorganic particle modifying process as surfactant；(3) silane coupled
Functional area, this part function are silane coupling agent, modifying agent can be connected on inorganic particle by the reactivity of silane.
Novel antioxygen silane coupling agent of this class containing hindered phenol structure combines inorganic filler modification and the addition of antioxidant
To together, not only have the advantages that the antioxidant effect of Hinered phenols antioxidant it is good, pollution it is small, not easy to change, less toxic or nontoxic,
Also there is the unique structure of silane coupling agent and performance, such as cementability, compatibility, dispersibility, considerably increase antioxidant with
The compatibility of high molecular material.In addition to this, the structure of single hindered phenol antioxygen is simple, passes through single hindered phenol after chemical modification
This Long carbon chain of increasing silane coupling agent, improves antioxidant relative molecular mass on the one hand in the molecular radical of antioxidant, increases
Add the stability of antioxidant, while enhancing the compatibility of inorganic filler and polymeric matrix.This class is containing hindered phenol structure
Novel antioxygen silane coupling agent combines inorganic particle modification procedure and addition antioxidant step together, can both reduce work
Sequence, and can ensure the evenly dispersed of antioxidant, also there is significant advantage in technique.Quaternary ammonium salt structure part is as surface
Activating agent can significantly reduce the surface energy of inorganic particle modifying process, reduce modification time.Such coupling agent also has this hair
Bright exclusive degrading resistance property is good, strong compatibility and the advantages that have a wide range of application.
The polyolefin of novel silane coupler modified calcium carbonate of the present invention containing hindered phenol has the following advantages：(1) even
Join agent modified calcium carbonate, significantly reduces the polarity of calcium carbonate, promote the dispersion of calcium carbonate.(2) by calcium carbonate modified step
Step is added with antioxidant to combine, reduces process.(3) design feature of the novel silane coupler containing hindered phenol can be with
Ensure that antioxidant recently, avoids antioxidant and disperse non-uniform weakness with filler distance.
Description of the drawings
Fig. 1 is raw material 2, and 6- DI-tert-butylphenol compounds (a), benzyl chloride hindered phenol (b), diethylin are for methyltriethoxy silane
Alkane (c), synthesis hindered phenol structure novel silane coupler (d) infrared spectrum (FT-IR)；
Fig. 2 is that the novel silane coupler of the hindered phenol structure containing quaternary ammonium salt of the synthesis synthesized in embodiment 1 (indicates in figure
For " quaternary ammonium salt "), raw material diethylin is for methyltriethoxysilane (being denoted as in figure " silane coupling agent "), raw material benzyl chloride
The thermogravimetric analysis figure (TG) of hindered phenol (being denoted as in figure " chloro hindered phenol ").
Specific implementation mode
In order to be better understood by the present invention, with reference to specific embodiment, the present invention is further illustrated, but this
The embodiment of invention is without being limited thereto.
Embodiment 1：
(1) benzyl chloride hindered phenolIt prepares identical as CN104744813A methods.
(2) synthesis of hindered phenol novel silane coupler：In N2Under protection, to equipped with mechanical agitation, condenser pipe, thermometer
250mL three-necked flask in above-mentioned 10 parts of synthesis benzyl chloride hindered phenol, 5 parts of dimethyl sulfoxide (DMSO)s, 10 parts of diethylin generations are added
MethyltriethoxysilaneOil temperature rises to 80 DEG C, reacts after 10-48h with 20 parts of petroleum ethers, 30 DEG C of vacuum
Dry 12h obtains hindered phenol novel silane coupler, is fractionated recycling design, is labeled as hindered phenol novel silane coupler 1
Infrared analysis (FT-IR, Fig. 1) and thermogravimetric (TG, Fig. 2) point are carried out to the hindered phenol novel silane coupler of synthesis
Analysis.Fig. 1 is analyzed, understands that in wave number be 2980cm by the curve a and b of Fig. 1-1The peak of left and right is that the flexible of H on phenyl ring shakes
Move peak, the wave number 746.5cm in curve b-1For the characteristic absorption peak of-C-Cl-.Benzyl chloride hindered phenol season can be learnt from curve d
Ammonium salt is in 2967.9cm-1The peak at place is the vibration absorption peak of C-H on phenyl ring, wave number 1139.0cm-1Place is the characteristic absorption of C-Si
Peak, wave number 795.7cm-1Place is the characteristic absorption peak of C-Cl, which exists in benzyl chloride hindered phenol, with silane coupling agent
The novel hindered phenol novel silane coupler of quaternary ammonium salt is formd, since quaternary ammonium salt anion part exists, causes C-Cl absorption peaks
By 746.5cm-1It is blue shifted to 795.7cm-1。
From Fig. 2 (TG figures) it is found that raw material diethylin (is denoted as " silane coupled for methyltriethoxysilane in figure
Agent ") decomposition temperature scope be 31.5-352.3 DEG C, temperature when decomposition rate is most fast is 50 DEG C.Raw material benzyl chloride hindered phenol
(being denoted as in figure " chloro hindered phenol ") is almost without weightlessness, the starting weightless temperature of benzyl chloride hindered phenol before 116.67 DEG C
116.67 DEG C, until 331 DEG C of whens decompose completely.The quaternary ammonium salt novel silane coupler (being denoted as in figure " quaternary ammonium salt ") of synthesis exists
Almost without weightlessness before 86.24 DEG C, starting weightless temperature is 86.24 DEG C, so between 86.24 DEG C -197.07 DEG C of temperature
Weightlessness both from the similar structure of silane coupling agent, and between 197.07 DEG C -352.29 DEG C weightlessness then come from benzyl
The similar structure of chlorine hindered phenol, but product quaternary ammonium salt novel silane coupler finally still have 10% or so it is residual it is heavy do not decompose, explanation
The fast decoupled property of the existing hindered phenol structure of quaternary ammonium salt novel silane coupler, inhibits the generation of free radical to reach antioxygen
Purpose；Have certain thermal stability again, be conducive to resist too fast decomposition in process, in addition, residual heavy part it may be said that
The presence of bright silane structure.It to sum up may be described as the novel silane coupler 1 that work(is prepared for hindered phenol structure.(2) hindered phenol
The application 1 (antioxygenic property) of the novel silane coupler of structure：0.5 part of above-mentioned conjunction is added into the calcium carbonate of 30 mass parts
At hindered phenol structure 1,60 DEG C of novel silane coupler high-speed stirred 30 minutes, add to 100 mass parts it is random altogether
Poly- polypropylene continues stirring 30 minutes, after squeezing out 1,2,3,4,5 time respectively on the twin screw extruder, surveys its melt index.
Double screw extruder temperature：One 190 DEG C of area, two 200 DEG C of areas, three 210 DEG C of areas, four 220 DEG C of areas, five 230 DEG C of areas, machine
First 225 DEG C.It is an area 55MPa, two area 50MPa, three that pellet, which will be squeezed out, in being molded obtained standard sample, injection pressure on injection molding machine
Area 45MPa, four area 40MPa.
Thermo oxidative aging performance is shown in Table 1.As can be seen from Table 1：0.5 part of hindered phenol novel silane coupler 1 of addition changes
Property calcium carbonate atactic copolymerized polypropene after squeezing out different number, the melt index of atactic copolymerized polypropene is almost without change
Change, illustrate that macromolecular chain is not influenced by heat and is largely broken, hindered phenol novel silane coupler have it is good it is anti-oxidant,
Degrading resistance property.With 30 parts of calcium carbonate of addition, the sample comparison of 0.5 part of antioxidant 1010, melt index is integrally less than normal, explanation
0.5 part of 1 antioxidant effect of hindered phenol novel silane coupler is better than 0.5 part of antioxidant 1010 (comparative example 2).
(2) application 2 (mechanical property) of the novel silane coupler of hindered phenol structure：Add into the calcium carbonate of 30 mass parts
1,60 DEG C of the novel silane coupler high-speed stirred 30 minutes for entering the hindered phenol structure of 0.5 part of above-mentioned synthesis, adds to 100
The atactic copolymerized polypropene of mass parts continues stirring 30 minutes, on the twin screw extruder extrusion mixing material, pelletizing.Twin-screw
Extruder temperature：One 190 DEG C of area, two 200 DEG C of areas, three 210 DEG C of areas, four 220 DEG C of areas, five 230 DEG C of areas, 225 DEG C of head.It will squeeze out
Pellet is an area 55MPa, two area 50MPa, three area 45MPa, 4th area in being molded obtained standard sample, injection pressure on injection molding machine
40MPa.Tensile property is tested 5, is made even by GB/T 1040.2-2006 tests, rate of extension 50mm/min, every group of batten
Mean value.Impact property is averaged by GB/T 1843-2008 tests, impact strength.
Add mechanical property such as 2 institute of table of the atactic copolymerized polypropene of 1 modified calcium carbonate of hindered phenol novel silane coupler
Show, as can be seen from Table 2：(1) the random total of modified calcium carbonate prepared by 0.5 part of hindered phenol novel silane coupler 1 is added
Poly- polyacrylic impact, the mechanical properties such as stretching, relatively to add unmodified calcium carbonate good, illustrates that silane coupling agent improves carbonic acid
The dispersion of calcium in the polymer, while improving the performance of material.It is even that (comparative example 1) (2) add 0.5 part of hindered phenol novel silane
Join agent modified calcium carbonate atactic copolymerized polypropene with addition 0.5 part of Silane coupling agent KH550 and modified sample power
Intensity contrast is learned, it is found that mechanical property promotes (comparative example 3).Illustrate, novel silane coupler is carried due to molecular chain length increase
The compatibility of high calcium carbonate and polymeric matrix is better than the silane hindered phenol novel silane coupler effect of traditional KH550.
Embodiment 2：
The present embodiment difference from Example 1 is temperature in the synthesis step (1) of hindered phenol novel silane coupler 1
90 DEG C, reaction time 8h are changed to, diethylin is changed to 12 parts for methyltriethoxysilane, and solvent dosage is 10 parts, petroleum ether
40 parts.Vacuum drying temperature is 25 DEG C, drying time 14h；(2) processing dispensing is changed to be added into the calcium carbonate of 30 mass parts
0.25 part of hindered phenol novel silane coupler, modifying process are 70 DEG C of high-speed stirreds 20 minutes.
Thermo oxidative aging performance is shown in Table 1.0.25 part of hindered phenol novel silane coupler is added as can be seen from Table 1 to be modified
After squeezing out different numbers, melt index slightly increases the atactic copolymerized polypropene of calcium carbonate, but changes less, illustrates nothing
The strand of rule copolymer polypropylene is slightly broken, but not influences its performance.
Mechanical property is shown in Table 2.Change to 0.25 part from table 2 it can be seen that reducing hindered phenol novel silane coupler 1 dosage
It is good that the mechanical properties such as impact, the stretching of atactic copolymerized polypropene of property calcium carbonate relatively add unmodified calcium carbonate, illustrates silane
Coupling agent improves the dispersion of calcium carbonate in the polymer, while improving the performance of material.
Embodiment 3：
This implementation difference from Example 1 is in the synthesis step (1) of hindered phenol novel silane coupler 1 that temperature changes
It it is 100 DEG C, reaction time 12h, diethylin is 15 parts for methyltriethoxysilane, and solvent is changed to 20 parts of toluene, petroleum ether
50 parts.Vacuum drying temperature is 45 DEG C, and drying time obtains for 10h；(2) processing dispensing is changed into the calcium carbonate of 30 mass parts
0.1 part of hindered phenol novel silane coupler 1 is added, modifying process is 80 DEG C of high-speed stirreds 25 minutes.
Thermo oxidative aging performance is shown in Table 1.0.1 part of hindered phenol novel silane coupler 1 is added as can be seen from Table 1 to be modified
After squeezing out different numbers, melt index slightly increases the atactic copolymerized polypropene of calcium carbonate, but changes less, illustrates nothing
The strand of rule copolymer polypropylene is slightly broken, but not influences its performance.
Mechanical property is shown in Table 2.Change to 0.1 part from table 2 it can be seen that reducing hindered phenol novel silane coupler 1 dosage
Than the 0.5 part hindered phenol novel silane coupler dosages of mechanical properties such as impact, the stretching of atactic copolymerized polypropene of property calcium carbonate
It is slightly decreased compared to performance, it is better than adding unmodified calcium carbonate, illustrate that silane coupling agent improves calcium carbonate in the polymer
Dispersion, while improving the performance of material.Add the silane coupling agent of 1 dosage of hindered phenol novel silane coupler to 0.1 part
The modified effect (comparative example 3) of the similar antioxidant effect of 0.5 part of antioxidant 1010 of addition and KH550 coupling agents can be reached,
Mechanical property is also preferable simultaneously.
Embodiment 4：
This implementation difference from Example 1 is to be changed to low density polyethylene (LDPE) using matrix
Thermo oxidative aging performance is shown in Table 1.The carbon of 0.5 part of hindered phenol novel silane coupler 1 is added as can be seen from Table 1
After squeezing out different numbers, melt index slightly increases the low density polyethylene (LDPE) of sour calcium, but changes less, illustrates low-density
The strand of polyethylene is slightly broken, but not influences its performance.
The mechanical property for adding the low density polyethylene (LDPE) of 1 modified calcium carbonate of hindered phenol novel silane coupler is as shown in table 2,
As can be seen from Table 2：The low density polyethylene of the calcium carbonate of 30 parts of addition (0.5 part of hindered phenol novel silane coupler 1 is modified)
The mechanical strength of alkene and the sample after the calcium carbonate of 30 parts of addition (0.5 part of KH550 is modified) and 0.5 part of antioxidant 1010 compares,
It was found that mechanical property promotes (comparative example 5).Illustrate, hindered phenol novel silane coupler 1 is improved since molecular chain length increases
The compatibility of calcium carbonate and polymeric matrix promotes the degree of scatter of calcium carbonate in a polymer matrix, therefore than tradition
KH550 silane coupling agents effect is good.
Embodiment 5：
This implementation difference from Example 1 is to be changed to polystyrene using matrix
Thermo oxidative aging performance is shown in Table 1.The carbon of 0.5 part of hindered phenol novel silane coupler 1 is added as can be seen from Table 1
After squeezing out different numbers, melt index slightly increases the polystyrene of sour calcium, but changes less, illustrates polystyrene
Strand is slightly broken, but not influences its performance.
The mechanical property for adding the polystyrene of 1 modified calcium carbonate of hindered phenol novel silane coupler is as shown in table 2, from table
It can be seen that in 2：The polystyrene and addition 30 of 30 parts of addition (0.5 part of hindered phenol novel silane coupler 1 is modified) calcium carbonate
The mechanical strength comparison of sample after part (0.5 part of KH550 is modified) calcium carbonate and 0.5 part of antioxidant 1010, finds mechanical property
It is promoted (comparative example 6).Illustrate, hindered phenol novel silane coupler 1 improves calcium carbonate and polymerize since molecular chain length increases
The compatibility of object matrix promotes the degree of scatter of calcium carbonate in a polymer matrix, therefore than traditional KH550 silane coupling agents
Effect is good.
Embodiment 6：
The present embodiment difference from Example 1 is raw material in the synthesis step (1) of hindered phenol novel silane coupler
Diethylin is changed to diethylin for methyltrimethoxysilane for methyltriethoxysilaneObtain product mark
It is denoted as hindered phenol novel silane coupler 2.
Thermo oxidative aging performance is shown in Table 1.30 parts of (0.5 part of hindered phenol novel silane couplers are added as can be seen from Table 1
2 are modified) after squeezing out different numbers, melt index slightly increases for the atactic copolymerized polypropene of calcium carbonate, but change it is little,
Illustrate that the strand of atactic copolymerized polypropene is slightly broken, but not influences its performance.
Mechanical property is shown in Table 2.From table 2 it can be seen that 30 parts of addition (0.5 part of hindered phenol novel silane coupler 2 is modified)
It is good that the mechanical properties such as impact, the stretching of the atactic copolymerized polypropene of calcium carbonate relatively add unmodified calcium carbonate, illustrates silane idol
Connection agent improves the dispersion of calcium carbonate in the polymer, while improving the performance of material.
Embodiment 7：
The present embodiment difference from Example 1 is raw material in the synthesis step (1) of hindered phenol novel silane coupler
Diethylin is changed to 3- (N, N- methylcyclohexyl amine) hydroxypropyl methyl dimethoxysilane for methyltriethoxysilane
Acquisition Product Labeling is hindered phenol novel silane coupler 3
Thermo oxidative aging performance is shown in Table 1.30 parts of (0.5 part of hindered phenol novel silane couplers are added as can be seen from Table 1
3 are modified) after squeezing out different numbers, melt index slightly increases for the atactic copolymerized polypropene of calcium carbonate, but change it is little,
Illustrate that the strand of atactic copolymerized polypropene is slightly broken, but not influences its performance.
Mechanical property is shown in Table 2.From table 2 it can be seen that 30 parts of addition (0.5 part of hindered phenol novel silane coupler 3 is modified)
It is good that the mechanical properties such as impact, the stretching of the atactic copolymerized polypropene of calcium carbonate relatively add unmodified calcium carbonate, illustrates silane idol
Connection agent improves the dispersion of calcium carbonate in the polymer, while improving the performance of material.
Embodiment 8：
The present embodiment difference from Example 1 is raw material in the synthesis step (1) of hindered phenol novel silane coupler
Diethylin is changed to N, N- dimethyl -3- aminopropyltriethoxy dimethoxysilanes for methyltriethoxysilane
Acquisition Product Labeling is hindered phenol novel silane coupler 4
Thermo oxidative aging performance is shown in Table 1.30 parts of (0.5 part of hindered phenol novel silane couplers are added as can be seen from Table 1
4 are modified) after squeezing out different numbers, melt index slightly increases for the atactic copolymerized polypropene of calcium carbonate, but change it is little,
Illustrate that the strand of atactic copolymerized polypropene is slightly broken, but not influences its performance.
Mechanical property is shown in Table 2.From table 2 it can be seen that 30 parts of addition (0.5 part of hindered phenol novel silane coupler 4 is modified)
It is good that the mechanical properties such as impact, the stretching of the atactic copolymerized polypropene of calcium carbonate relatively add unmodified calcium carbonate, illustrates silane idol
Connection agent improves the dispersion of calcium carbonate in the polymer, while improving the performance of material.
Embodiment 9：
It is 0.75 part that the present embodiment difference from Example 1 hindered phenol novel silane coupler, which is modified dosage, calcium carbonate
It is 45 parts that dosage, which increases,
Thermo oxidative aging performance is shown in Table 1.As can be seen from Table 1：40 parts of addition (0.67 part of hindered phenol novel silane coupling
Agent 4 is modified) atactic copolymerized polypropene of the atactic copolymerized polypropene of calcium carbonate is after squeezing out different numbers, random copolymerization poly- third
The melt index of alkene is almost unchanged, illustrates that macromolecular chain is not influenced by heat and is largely broken, and hindered phenol novel silane is even
Joining agent has good anti-oxidant, degrading resistance property.
Mechanical property is shown in Table 2.From table 2 it can be seen that 40 parts of addition (0.67 part of hindered phenol novel silane coupler 4 is modified)
It is good that the mechanical properties such as impact, the stretching of the atactic copolymerized polypropene of calcium carbonate relatively add unmodified calcium carbonate, illustrates silane idol
Connection agent improves the dispersion of calcium carbonate in the polymer, while improving the performance of material.
Comparative example 1：
To the atactic copolymerized polypropene of 100 mass parts be added 30 parts of calcium carbonate, on the twin screw extruder respectively squeeze out 1,
2, after 3,4,5 times, its melt index is surveyed；It squeezes out on the twin screw extruder, be molded detection impact, tensile property.
Comparative example 2：
30 parts of calcium carbonate, 0.5 part of antioxidant 1010, in twin-screw is added to the atactic copolymerized polypropene of 100 mass parts
After squeezing out 1,2,3,4,5 time on extruder respectively, its melt index is surveyed；On the twin screw extruder squeeze out, be molded detection impact,
Tensile property.
Comparative example 3：
30 parts of (0.5 part of KH550 is silane coupler modified) calcium carbonate are added to the atactic copolymerized polypropene of 100 mass parts,
0.5 part of antioxidant 1010 surveys its melt index after squeezing out 1,2,3,4,5 time respectively on the twin screw extruder；It is squeezed in twin-screw
Go out on machine to squeeze out, be molded detection impact, tensile property.
Comparative example 4：
Being added 30 parts to the atactic copolymerized polypropene of 100 mass parts, (0.5 part of diethylin is for methyltriethoxysilane idol
Join agent to be modified) calcium carbonate, after squeezing out 1,2,3,4,5 time respectively on the twin screw extruder, it is molten to survey it 0.5 part of antioxidant 1010
Melt index；It squeezes out on the twin screw extruder, be molded detection impact, tensile property.
Comparative example 5：
To the low density polyethylene (LDPE) of 100 mass parts be added 30 parts of (0.5 part of KH550 is silane coupler modified) calcium carbonate, 0.5
Part antioxidant 1010 surveys its melt index after squeezing out 1,2,3,4,5 time respectively on the twin screw extruder；In twin-screw extrusion
It squeezed out on machine, be molded detection impact, tensile property.
Comparative example 6：
30 parts of (0.5 part of KH550 is silane coupler modified) calcium carbonate are added to the polystyrene of 100 mass parts, 0.5 part anti-
Oxygen agent 1010 surveys its melt index after squeezing out 1,2,3,4,5 time respectively on the twin screw extruder；On the twin screw extruder
It squeezes out, injection molding detection is impacted, tensile property.
Comparative example 7：
40 parts of (0.67 part of KH550 is silane coupler modified) calcium carbonate are added to the atactic copolymerized polypropene of 100 mass parts,
0.5 part of antioxidant 1010 surveys its melt index after squeezing out 1,2,3,4,5 time respectively on the twin screw extruder；It is squeezed in twin-screw
Go out on machine to squeeze out, be molded detection impact, tensile property.
1 polyolefin of table repeatedly processes melt index variation
2 polymer impact tensile property of table
Claims (6)
1. a kind of polyolefin of the novel silane coupler modified calcium carbonate containing hindered phenol, it is characterised in that：To 30-40 mass parts
Calcium carbonate in be added 0.1-1 parts hindered phenol structure novel silane coupler, 60 DEG C of -80 DEG C of high-speed stirreds 20-30 minutes,
Add the polyolefin to 100 mass parts, continue stirring 30 minutes, squeeze out on the twin screw extruder to get.
2. a kind of polyolefin of novel silane coupler modified calcium carbonate containing hindered phenol according to claim 1, special
Sign is：The polyolefin is atactic copolymerized polypropene, polyethylene or polystyrene.
3. a kind of polyolefin of novel silane coupler modified calcium carbonate containing hindered phenol according to claim 1, special
Sign is：The double screw extruder temperature：One 190 DEG C of area, two 200 DEG C of areas, three 210 DEG C of areas, four 220 DEG C of areas, five areas 230
DEG C, 225 DEG C of head；It is an area 55MPa, 2nd area that pellet, which will be squeezed out, in being molded obtained standard sample, injection pressure on injection molding machine
50MPa, three area 45MPa, four area 40MPa.
4. a kind of polyolefin of novel silane coupler modified calcium carbonate containing hindered phenol according to claim 1, special
Sign is：The novel silane coupler structural formula containing hindered phenol is：
,
Wherein, R1 is methyl, ethyl or propyl, and R2 is methyl, ethyl, propyl or cyclohexyl, n 1-4.
5. a kind of polyene of novel silane coupler modified calcium carbonate containing hindered phenol according to one of claim 1-4
Hydrocarbon, it is characterised in that：The preparation method of the novel silane coupler containing hindered phenol：In N2Under protection, 2,6- bis- tertiary fourths
After base -4- (chloromethyl) phenol, dimethyl sulfoxide and the silane coupling agent containing tertiary amine group react 8-48h at 80-100 DEG C,
Washing, vacuum drying obtain the novel antioxygen silane coupling agent containing hindered phenol structure.
6. a kind of polyolefin of novel silane coupler modified calcium carbonate containing hindered phenol according to claim 5, special
Sign is：The silane coupling agent containing tertiary amine group includes diethylin for methyltriethoxysilane, diethylin
For methyltrimethoxysilane, 3- (N, N- methylcyclohexyl amine) hydroxypropyl methyl dimethoxysilanes and N, N- dimethyl -3- ammonia
Hydroxypropyl methyl dimethoxysilane.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100384A (en) * | 2019-12-30 | 2020-05-05 | 贵州师范大学 | Novel hindered phenol-containing silane coupling agent modified calcium carbonate polyolefin and preparation method thereof |
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| US4374742A (en) * | 1978-08-18 | 1983-02-22 | Ciba-Geigy Corporation | Novel lubricant additives |
| CN1978553A (en) * | 2005-12-02 | 2007-06-13 | 中国科学院化学研究所 | Surface grafting organic functional molecular nano silicon dioxide, and its preparing method |
| CN107857897A (en) * | 2017-10-30 | 2018-03-30 | 华南理工大学 | A kind of hindered phenol functionalization graphene and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4374742A (en) * | 1978-08-18 | 1983-02-22 | Ciba-Geigy Corporation | Novel lubricant additives |
| CN1978553A (en) * | 2005-12-02 | 2007-06-13 | 中国科学院化学研究所 | Surface grafting organic functional molecular nano silicon dioxide, and its preparing method |
| CN107857897A (en) * | 2017-10-30 | 2018-03-30 | 华南理工大学 | A kind of hindered phenol functionalization graphene and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111100384A (en) * | 2019-12-30 | 2020-05-05 | 贵州师范大学 | Novel hindered phenol-containing silane coupling agent modified calcium carbonate polyolefin and preparation method thereof |
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Application publication date: 20180904 |