CN105175595B - A kind of alkylsiloxane olefin random copolymer and its preparation method and application - Google Patents
A kind of alkylsiloxane olefin random copolymer and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of alkylsiloxane olefin random copolymer and its preparation method and application, shown in the structure such as formula (I) of the alkylsiloxane olefin random copolymer, wherein R is C1‑C8Alkyl or phenyl, the value of " m " is 1.5~200, and the value of " n " is 150~2000, and the value of " m/n " is 0.01~0.1, and " a " is the integer between 0 to 8, and " b " is the integer between 1 to 9, and " c " is the integer between 0 to 8.Such alkylsiloxane olefin random copolymer can effectively improve the mobile performance of product as polyolefin modifier, not influence even to improve its mechanical property.
Description
Technical field
The invention belongs to modifier field, and in particular to a kind of alkylsiloxane-olefin random copolymer and its system
Preparation Method and application.
Background technology
Polysiloxanes high and low temperature resistance is excellent, surface tension is extremely low, dielectric properties are good, can as modifier,
Surface modifier, fire retardant etc., have broad application prospects.Yet with the compatibility between polysiloxanes and carbon-based material
Difference, polysiloxanes is easily migrated to material surface；And polysiloxanes mechanical performance is poor, the comprehensive of material may be influenceed
Can, these factors hinder its application in field of plastics processing.
Polyolefin is cheap, combination property is good, is the maximum general-purpose plastics of consumption.By polysiloxanes and polyolefin knot
Close, form the blend or copolymer of polysiloxanes-polyolefin, can effectively improve its compatibility with carbon-based material, and
And the performance characteristics of polysiloxanes and polyolefin can be had concurrently, with far-reaching Research Significance.
Blend or copolymer that kinds of schemes prepares polysiloxanes-polyolefin has been proposed.DOW CORNING
Multibase series of products, are blended (50/50) and prepare masterbatch by polysiloxanes and the polyolefin carrier of super high molecular weight
Grain, overcomes polysiloxanes and easily migrates to the shortcoming of material surface, can be used as the processing aid of polyolefin.However, due to poly-
Siloxanes is extremely incompatible with polyolefin, and blend lacks chemical bonding effect, and the phase separation of this kind of product is brighter than copolymer
It is aobvious, cause its improvement to be limited.
The A1 of WO 1995000578 disclose a kind of siloxanes-olefin copolymer, and the free radical by functional groups is anti-
Should prepare.Because the reaction efficiency between polysiloxane macromonomer and polyolefin macromolecular is relatively low, and reaction temperature is higher by (150
DEG C~350 DEG C), it is unfavorable for the accuracy controlling of product structure.
WO2012103080A1 reports a kind of polyolefin-polysiloxane block copolymers, by aluminium be coordinated polyolefin with
It is prepared by the coupling reaction of polysiloxanes.The temperature of coupled reaction is (150 DEG C) higher, the molecular weight distribution (PDI=wider of copolymer
5~6), the control of product structure is unsatisfactory.
We once disclosed a kind of polyalkylsiloxane-polyolefin block copolymer (CN104672463A), by poly- alkane
Radical siloxane is prepared with the hydrosilylation of polyolefin.This kind of copolymer structure easily regulates and controls, and the stream as polyolefin
Dynamic modifying agent, there is preferable modified effect.
Summary document understands that polysiloxanes-polyolefin copolymer is the important processing aid of a class, its preparation method
It is mostly the relatively low radical polymerization of reaction efficiency.If can with industrial wide variety of coordination polymerization technology realize alkene with
The controllable combined polymerization of siloxanyl monomers, the novel silicone-olefin copolymer of excellent will have very great meaning
Justice.However, because the polarity of siloxanyl monomers is stronger, easily poisoning transition-metal catalyst inactivates it, thus alkene and biography
The Coordination copolymerization of system siloxanes closes still very challenging property.
The content of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, primary and foremost purpose of the invention is to provide a kind of alkyl silica
Alkane-olefin random copolymer, the copolymer is synthesized by industrial wide variety of coordination polymerization technology, and structure is easy to control
System, works well as modifier.
Another object of the present invention is to provide a kind of preparation method of abovementioned alkyl siloxanes-olefin random copolymer.
It is still another object of the present invention to provide abovementioned alkyl siloxanes-olefin random copolymer in polyolefin manufacture field
Application.
A kind of polyalkylsiloxane-polyolefin block copolymer, shown in structure such as formula (I)：
In formula (I), R is C1-C8Alkyl or phenyl, the value of " m " is 1.5~200, and the value of " n " is 150~2000, " m/n "
Value be 0.01~0.1, " a " is the integer between 0 to 8, and " b " is the integer between 1 to 9, and " c " is the integer between 0 to 8.
An essential characteristic of the invention is that have 4~12 siloxane branches of carbon atom straight chain alkyl and polyolefin master
Chain simultaneously exist, and these groups quantity, distribution and property.
Preferably, in formula (I), R is methyl or phenyl, and the value of " m " is 4~80；The value of " n " is 200~1000, " m/n "
Value be 0.02~0.08, " a " is the integer between 2 to 6, and " b " is the integer between 1 to 4, and " c " is the integer between 2 to 6.
Alkylsiloxane component be formula (I) in the degree of polymerization for m repeat unit summation, polyolefin component be formula (I) in
The degree of polymerization is the summation of the repeat unit of n.Based on the mole of the alkylsiloxane-olefin random copolymer, the alkyl
The degree of silicone components is 1%~9.1%.
Present invention also offers a kind of preparation method of described alkylsiloxane-olefin random copolymer, including：
(1) in the presence of hydrosilylation catalyst, there is silicon hydrogen in excessive double hydrogen endcapped siloxanes with linear alpha-olefin
Addition reaction, the alkylsiloxane of the single hydrogen end-blocking of generation.
Shown in the structure of described polysiloxanes such as formula (II)：
(2) in the presence of hydrosilylation catalyst, the alkylsiloxane and excessive straight chain alpha, ω-diene of single hydrogen end-blocking
There is hydrosilylation, the alkylsiloxane of generation double bond end-blocking in hydrocarbon.
Shown in the structure of described alkylsiloxane such as formula (III)：
In formula (II) and (III), R is C1-C8Alkyl or phenyl, " a " is the integer between 0 to 8, and " b " is between 1 to 9
Integer, " c " is the integer between 0 to 8.
(3) in the presence of transition-metal catalyst, the alkylsiloxane and alkene generation Coordination copolymerization of double bond end-blocking are anti-
Should, alkylsiloxane-olefin random copolymer is generated, as shown in formula (I).
The alkylsiloxane obtained using the preparation method-olefin random copolymer molecular structure is easily controllable, Er Qiefen
Son amount is higher, and heat endurance is more preferable.
Preferably, described hydrosilylation catalyst is platinum catalyst, for example：Karstedt catalyst；Transition metal
Catalyst is Ziegler-Natta catalyst.The hydrosilylation catalyst of step (1) and step (2) is usually identical, works as step
Suddenly when remaining hydrosilylation catalyst is active enough in (1), step (2) can also be not added with.
Double hydrogen endcapped siloxanes are 2/1~10/1 with the material molar ratio of linear alpha-olefin, the alkyl silica of single hydrogen end-blocking
Alkane and straight chain alpha, the material molar ratio of ω-alkadienes is 1/2~1/10, and the alkylsiloxane of double bond end-blocking and the raw material of alkene are dense
Degree is than being 1/0.1~1/10.
The temperature of hydrosilylation is 30~90 DEG C, and the reaction time is 4~12h.The temperature of Coordination copolymerization reaction is 30
~80 DEG C, the reaction time is 5~60min.
The compounds of this invention has as the property desired by processing aid.Present invention also offers a kind of described alkyl
The application in polyolefin manufacture field of siloxanes-olefin random copolymer.Described alkylsiloxane-olefin random copolymerization
Thing as polyolefin modifier, to improve processing characteristics and mechanical property, addition for polyolefin quality 0.5~
10%.
Compared with the existing technology, beneficial effects of the present invention are embodied in：
The present invention innovatively uses the relatively low alkylsiloxane of polarity as co-monomer, by Ziegler-
Natta catalyst carries out Coordination copolymerization, synthesis of alkyl siloxanes-olefin random copolymer with alkene.The structure of gained copolymer
It is easy to regulation and control, the compatibility with carbon-based material is preferable, and surface tension is low, and strand compliance is good, hence for polyolefin
Mobile performance and mechanical property have preferable modified effect.
Brief description of the drawings
Fig. 1 is the high temperature nuclear-magnetism hydrogen spectrogram of the gained copolymer of embodiment 1.
Specific embodiment
The present invention is better understood with by following embodiments.There is provided these embodiments to be for the purpose of illustration, and be not intended to
Limitation the scope of the present invention.
Embodiment 1
(1) it is provided with the 250mL flasks of magnetic stir bar, condensation reflux device and air inlet pipe to one, adds 92g
(0.69mol) tetramethyl disiloxane, 25.6g (0.23mol) 1- octenes and 50g toluene.After device is full of nitrogen, add
0.067g (30ppm) Karstedt catalyst solutions (mass concentration of platinum is 2%), are heated to 60~80 DEG C and stir 8h.Dress
After putting cooling, post processing removes unreacted tetramethyl disiloxane, toluene and Karstedt catalyst, the water white transparency for obtaining
Liquid is the alkylsiloxane of single hydrogen end-blocking.Conversion ratio is 47%.Characterized from nucleus magnetic hydrogen spectrum, the alkyl silicon of single hydrogen end-blocking
In oxygen alkane, b=1, c=4.
(2) alkylsiloxane of the single hydrogen end-blocking for obtaining 50g (0.2mol) step (1), 67.1g (0.61mol) 1,7-
Octadiene and 50g toluene are added to one and are provided with the flask of agitator, condensation reflux device, air inlet pipe, when device is full of nitrogen
After atmosphere is enclosed, it is heated to 60~80 DEG C and stirs 10h.After device cooling, post processing removes unreacted 1,7- octadienes, toluene
With Karstedt catalyst, the alkylsiloxane of the colourless transparent liquid for obtaining as double bond end-blocking.Conversion ratio is 60%.By core
Magnetic hydrogen stave is levied and understood, in the alkylsiloxane of double bond end-blocking, a=4, b=1, c=4.
(3) 250mL there-necked flask nitrogen pump drainage, the high-temperature baking of mechanical agitation oar will be installed to remove water oxygen, is continued
Ethylene gas are passed through, 100mL toluene is added, stirring at low speed in 30~80 DEG C of water-baths is placed in.Add a certain amount of co-catalyst (alkane
Base aluminium, alkylaluminoxane or borine) and 5.7g (160mmol/L) double bond end-blocking alkylsiloxane, finally in strong agitation
1 μm of ol Ziegler-Natta vanadium series catalyst of lower addition.It is 1 atmospheric pressure to be continually fed into ethene and keep ethylene pressure.Instead
After answering 5~20min, 10% (V/V) acidic ethanol terminating reaction is added.Reaction solution is poured into 800mL acidic ethanols and stirs 5h,
Washed three times with dimethylbenzene and toluene after filtering, 12h is vacuum dried at 60 DEG C, obtain product by nucleus magnetic hydrogen spectrum and infrared spectrum
Turn out to be the random copolymer with alkylsiloxane side chain and alkene main chain.From nmr analysis, alkyl in the copolymer
The molar content of silicone components is 4.2%.Determined by gpc analysis, the copolymer has the Mw of 52600g/mol.
Embodiment 2
The step of repeating embodiment 1, is 11.4g except step (3) adds the amount of the alkylsiloxane of double bond end-blocking
(320mmol/L).Final product is turned out to be with alkylsiloxane side chain and alkene main chain by nucleus magnetic hydrogen spectrum and infrared spectrum
Random copolymer.From nmr analysis, the molar content of alkylsiloxane component is 7.8% in the copolymer.By GPC points
Analysis is determined, and the copolymer has the Mw of 42400g/mol.
Embodiment 3
The step of repeating embodiment 1, except the siloxanes of addition in step (1) is the silica of 1,1,3,3,5,5- hexamethyl three
Alkane (143.5g, 0.69mol).Step (1) product is the alkylsiloxane of single hydrogen end-blocking.Conversion ratio is 45%.By nuclear-magnetism hydrogen
Stave is levied and understood, in the alkylsiloxane of single hydrogen end-blocking, b=2, c=4.
The addition of the alkylsiloxane of single hydrogen end-blocking is changed into 63.7g (0.2mol) in step (2).Step (2) product is
It is the alkylsiloxane of double bond end-blocking.Conversion ratio is 57%.Characterized from nucleus magnetic hydrogen spectrum, the alkylsiloxane of double bond end-blocking
In, a=4, b=2, c=4.
The addition of the alkylsiloxane of double bond end-blocking is changed into 6.9g (160mmol/L) in step (3).Final product passes through
Nucleus magnetic hydrogen spectrum and infrared spectrum turn out to be the random copolymer with alkylsiloxane side chain and alkene main chain.Can by nmr analysis
Know, the molar content of alkylsiloxane component is 3.8% in the copolymer.Determined by gpc analysis, the copolymer has
The Mw of 48700g/mol.
Embodiment 4
The step of repeating embodiment 1, except addition alpha-olefin is 1- decene (32.3g, 0.23mol) in step (1).Step
(1) product is the alkylsiloxane of single hydrogen end-blocking.Conversion ratio is 48%.Characterized from nucleus magnetic hydrogen spectrum, the alkane of single hydrogen end-blocking
In radical siloxane, b=1, c=6.
The addition of the alkylsiloxane of single hydrogen end-blocking is changed into 54.9g (0.2mol), the α of addition, ω-two in step (2)
Alkene is 1,9- decadinene (83.0g, 0.6mol).Step (2) product is the alkylsiloxane of double bond end-blocking.Conversion ratio is
58%.Characterized from nucleus magnetic hydrogen spectrum, in the alkylsiloxane of double bond end-blocking, a=6, b=1, c=6.
The addition of the alkylsiloxane of double bond end-blocking is changed into 6.6g (160mmol/L) in step (3).Final product passes through
Nucleus magnetic hydrogen spectrum and infrared spectrum turn out to be the random copolymer with alkylsiloxane side chain and alkene main chain.Can by nmr analysis
Know, the molar content of alkylsiloxane component is 4.0% in the copolymer.Determined by gpc analysis, the copolymer has
The Mw of 58100g/mol.
Embodiment 5
The step of repeating embodiment 1, except the siloxanes of addition in step (1) is 1,1,5,5- tetramethyl -3,3- hexichol
Base trisiloxanes (229.5g, 0.69mol).Step (1) product is the alkyl phenyl silicones of single hydrogen end-blocking.Conversion ratio is
43%.Characterized from nucleus magnetic hydrogen spectrum, in the alkyl phenyl silicones of single hydrogen end-blocking, b=2, c=4 are connected with middle silicon atom
Two R bases be phenyl.
The addition of the alkyl phenyl silicones of single hydrogen end-blocking is changed into 88.6g (0.2mol) in step (2).Step (2) is produced
Thing is the alkyl phenyl silicones of double bond end-blocking.Conversion ratio is 54%.Characterized from nucleus magnetic hydrogen spectrum, the alkyl of double bond end-blocking
In siloxanes, a=4, b=2, c=4, two R bases being connected with middle silicon atom are phenyl.
The addition of the alkyl phenyl silicones of double bond end-blocking is changed into 8.9g (160mmol/L) in step (3).Final product
The random copolymer with alkyl phenyl silicones side chain and alkene main chain is turned out to be by nucleus magnetic hydrogen spectrum and infrared spectrum.By core
Magnetic analysis understands that the molar content of alkylsiloxane component is 3.4% in the copolymer.Determined by gpc analysis, copolymer tool
There is the Mw of 47500g/mol.
Method for assessing copolymer bulk properties
Glass transition temperature, crystallization temperature, fusing point and the melting of sample are measured using differential scanning calorimeter (Q200, TA)
Enthalpy, the heat endurance of sample is measured using thermogravimetric analyzer (Q500, TA).Measurement result is shown in Table 1.
The hot property of the copolymer of the embodiment 1~5 of table 1
From the result of table 1 it was determined that the copolymer of embodiment 1-5 has extremely low glass transition temperature, relatively low crystallization
Temperature, fusing point, less melting enthalpy and good heat endurance.With the increase of alkylsiloxane content, the glass of copolymer
Glass temperature reduction, crystallization temperature reduction, fusing point is lower, and melting enthalpy reduces.When siloxanes segment is more long in alkylsiloxane
(embodiment 3), the glass transition temperature of copolymer is especially low.This shows that alkylsiloxane segment can significantly improve the molecule of copolymer
Chain compliance, when alkylsiloxane side chain is more or siloxanes segment is more long, effect is more obvious.
Method for assessing copolymer-modified effect
100 parts of HDPE (trade mark S5000), the copolymer of 2.5~10 parts of embodiment 1-5,0.1 part of antioxidant (1010) are existed
200 DEG C, melt blending 20min under the conditions of 100rpm.The fusing point of sample is measured using differential scanning calorimeter (Q200, TA) and melt
Melt enthalpy (10 DEG C/min of heating rate).Using fusion index instrument (CE Λ ST) measure gained blend melt index (190 DEG C,
2.16kg).Tensile property (the GB/T of gained blend is measured using universal testing machine (Zwick/Roell Z020)
1040.3-2006)。
Comparative example
Commercially available super high molecular weight siloxanes masterbatch MB 50 is blended with HDPE under the same conditions, blend is then measured
Correlated performance, and with embodiment 1-5 contrast, the results are shown in Table 2.
Table 2
As can be known from the results of Table 2, the copolymer of embodiment 1~5 all improves significantly effect to the mobile performance of HDPE,
Influence of the addition of copolymer to the tensile strength and hot property of HDPE simultaneously is little.The modified effect of embodiment 2 and embodiment 3
Significantly, this shows within the specific limits, and alkylsiloxane side chain is more in copolymer, siloxanes segment is more long, its flowing
Modified effect is better.In addition, the elongation at break of embodiment 1~5 is all higher than HDPE, this shows that the addition of copolymer can be improved
The tear resistance of HDPE.The tensile strength of embodiment 5 is higher than HDPE, shows the introducing of phenyl and can improve the mechanical property of material.
In comparative example, the mobile performance of blend makes moderate progress compared with HDPE, but modified effect is not so good as embodiment 1~5, and blending
The tensile strength and elongation at break of thing have all declined.Result above shows, the modified effect of the copolymer of embodiment 1~5,
There is comprehensive advantage compared to comparative example.
Although the present invention has been described some implementation methods, it will be understood by those skilled in the art that providing these
Implementation method is merely to illustrate, and can carry out various modifications, change, replacement and equivalent embodiments without departing from this hair
Bright scope.Therefore, scope and spirit of the present invention only should be limited by claim and its equivalent form of value.
Claims (7)
1. a kind of alkylsiloxane-olefin random copolymer, it is characterised in that shown in structure such as formula (I)：
In formula (I), R is C1-C8Alkyl or phenyl, the value of " m " is 1.5~200, and the value of " n " is 150~2000, the value of " m/n "
It is 0.01~0.1, " a " is the integer between 0 to 8, " b " is the integer between 1 to 9, " c " is the integer between 0 to 8；
The preparation method of the alkylsiloxane-olefin random copolymer, including：
(1) in the presence of hydrosilylation catalyst, there is hydrosilylation in double hydrogen endcapped siloxanes, raw with linear alpha-olefin
Into the alkylsiloxane of single hydrogen end-blocking；
Shown in the structure such as formula (II) of the alkylsiloxane of described single hydrogen end-blocking：
(2) in the presence of hydrosilylation catalyst, there is silicon hydrogen in the alkylsiloxane and straight chain alpha of single hydrogen end-blocking, ω-alkadienes
Addition reaction, the alkylsiloxane of generation double bond end-blocking；
Shown in the structure such as formula (III) of the alkylsiloxane of described double bond end-blocking：
In formula (II) and (III), R is C1-C8Alkyl or phenyl, the value of " m " is 1.5~200, and the value of " n " is 150~2000, " m/
The value of n " is 0.01~0.1, and " a " is the integer between 0 to 8, and " b " is the integer between 1 to 9, and " c " is whole between 0 to 8
Number；
(3) in the presence of transition-metal catalyst, there is Coordination copolymerization reaction in the alkylsiloxane and alkene of double bond end-blocking, raw
Into described alkylsiloxane-olefin random copolymer.
2. alkylsiloxane-olefin random copolymer according to claim 1, it is characterised in that R is methyl or phenyl,
The value of " m " is 4~80；The value of " n " is 200~1000, and the value of " m/n " is 0.02~0.08, and " a " is the integer between 2 to 6,
" b " is the integer between 1 to 4, and " c " is the integer between 2 to 6.
3. alkylsiloxane-olefin random copolymer according to claim 1, it is characterised in that based on the alkyl silicon
The mole of oxygen alkane-olefin random copolymer, the degree of alkyl siloxane unit is 1%~9.1%.
4. alkylsiloxane-olefin random copolymer according to claim 1, it is characterised in that described Si―H addition reaction
Catalyst is platinum catalyst, and transition-metal catalyst is Ziegler-Natta catalyst.
5. alkylsiloxane-olefin random copolymer according to claim 1, it is characterised in that the alkyl of single hydrogen end-blocking
Siloxanes and straight chain alpha, the material molar ratio of ω-alkadienes is 1/2~1/10, alkylsiloxane and the original of alkene that double bond is blocked
Material molar concentration rate is 1/0.1~1/10.
6. a kind of being processed in polyolefin for alkylsiloxane-olefin random copolymer as described in any one of claims 1 to 3 is led
Application in domain.
7. the application in polyolefin manufacture field of alkylsiloxane-olefin random copolymer according to claim 6,
Characterized in that, described alkylsiloxane-olefin random copolymer is used as polyolefin modifier, addition accounts for gross weight
0.5~10%.
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| CN111363102B (en) * | 2020-03-18 | 2021-06-01 | 浙江大学 | Ethylene-alpha olefin-polyfluorosiloxane ternary graft copolymer and preparation method thereof |
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