CN107540843A - The function additive of side base containing chain alkyl and epoxy based polysiloxane and preparation method thereof - Google Patents
The function additive of side base containing chain alkyl and epoxy based polysiloxane and preparation method thereof Download PDFInfo
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- CN107540843A CN107540843A CN201710768037.2A CN201710768037A CN107540843A CN 107540843 A CN107540843 A CN 107540843A CN 201710768037 A CN201710768037 A CN 201710768037A CN 107540843 A CN107540843 A CN 107540843A
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Abstract
The invention discloses the function additive of side base containing chain alkyl and epoxy based polysiloxane and preparation method thereof；The function additive is colourless transparent oil liquid, and viscosity is 200~5000cSt, and the modification to polyolefin plastics has lubrication scattered and anti-scratch effect.During preparation, long-chain unsaturated olefin, allyl glycidyl ether and isopropyl alcohol solution of chloroplatinic acid are well mixed, 75 DEG C~85 DEG C is heated to, insulation activation, obtains chloroplatinic acid monomer complex；Nitrogen is passed through in gained chloroplatinic acid monomer complex, adds toluene and antioxidant, is warming up to 80 DEG C~90 DEG C, containing hydrogen silicone oil is added dropwise, continues 3~6h of reaction after dripping, removes low-boiling-point substance, temperature is improved to 110~120 DEG C, removes low-boiling-point substance, obtain product.Function additive of the present invention avoids migration problem existing for common silicone oil well, while retains that the basic lubrication of silicone oil is scattered, bright anti-scratch effect, has and lubricates the function such as scattered, anti-scratch.
Description
Technical field
The present invention relates to the function additive of a kind of side base containing chain alkyl and epoxy based polysiloxane and preparation method thereof,
The function additive is used for for example inorganic particle filled modification of modification of polyolefin plastics, has and lubricates the effect such as scattered, anti-scratch.
Background technology
Modification of the dimethyl silicone polymer to polyolefin plastics has the effects such as interior lubrication and the demoulding, the low liquid of molecular weight
Dimethyl silicone polymer (being commonly called as silicone oil) due to the plastics incompatibility such as polyolefin, it is easy to migrate to frosting and sprawl
Open, make surface greasy, reduce product surface japanning, the firmness of printing.The poly dimethyl silicon of molecular weight height (between 80-95 ten thousand)
Oxygen alkane replaces common low viscosity or moderately viscous silicone oil, and its higher viscosity has delayed mobile enrichment to surface to a certain extent
Speed, higher yet with molecular weight, drawing again can not dosing, it is difficult to uses etc. and lacks in the continuous hybrid process of plastics
Fall into.End hydroxyl silicone oil is also commonly used for the modification of inorganic particle filled polyolefin plastics, and the terminal hydroxy group of a small amount of polarity can certain journey
Interaction between the increase inorganic filler of degree ground and non-polar polyolefinic, but effect is extremely limited.Therefore, in low viscosity or medium
After the dimethyl silicone polymer side base of viscosity introduces epoxy radicals, chain alkyl etc. simultaneously, when epoxy radicals and chain alkyl mol ratio
When in particular range, as the modified processing aid of polyolefin plastics (polypropylene, polyethylene etc.), particularly in inorganic particulate
When enhancing, fire-retardant or conductive filler, have and lubricate dispersiveness between increase plastic substrate, filler or other additives, promote to make
The smooth and anti-scratch effect in product surface, due to having compared with strong interaction with polyolefin plastics, inorganic particulate etc., during use not
Easily to surface migration, robust consistent.
On dimethyl silicone polymer side base it is modified in terms of report that more changed with chain alkyl or epoxy radicals at present
Property Hydrophilicrto polyether silicone oil, to improve emulsibility, defoaming and textile finishing function etc..(chain alkyl and the polyethers such as Wang Anqi
The synthesis of comodified polysiloxane and its application in defoamer, printing and dyeing assistant, 2014 (10)：20-23) gathered using allyl alcohol
Ether, laurylene and silicon oil of low hydrogen content reaction are prepared for a kind of chain alkyl and hydrophilic polyether modified silicone oil, and its structural formula is as follows：
After chain alkyl introducing, hydrophobicity increases the modified silicon oil, assigns its good antifoam performance, but due to ether
Content is very high, causes it to be interacted with inorganic filler particle and increases, and makes silicone oil migration less than surface or migration velocity
Slow down significantly, so as to inorganic particulate enhancing, the no obvious anti-scratch effect of fire-retardant or conductive filler improved polyalkene.
It is resistance to as amido silicon oil that Chinese invention patent (CN102505496A) discloses a kind of epoxy radicals polyether modified silicon oil
Long property hydrophilic potentiating agent.Its structural formula is as follows：
The silicone oil side base contains polyethers and epoxy radicals, and hydrophily is very strong, is used as hydrophilic potentiating agent；But due to and be free of
There is a hydrophobic oleophilic oil group such as chain alkyl, therefore it is very weak to interact with polyolefin, do not have an anchorage effect, therefore can not be
Played in inorganic particle filled improved polyalkene system and lubricate the effect such as scattered, anti-scratch well.
The content of the invention
It is an object of the invention to provide a kind of chain alkyl and epoxy based polysiloxane function additive, it is used for inorganic
When particulate reinforcement, fire-retardant or conductive filler improved polyalkene, have that lubrication is scattered, the smooth function such as anti-scratch in surface；
Another object of the present invention is to provide function additive of the side base containing chain alkyl and epoxy based polysiloxane
Preparation method.
In the prior art, modifying plastics auxiliary agent is used as not yet with long-chain olefin and propyl glycidyl ether base co-modified silicone oil
Appear in the newspapers.It is anti-that Si―H addition reaction can occur under platinum catalysis with containing hydrogen silicone oil for long-chain unsaturated olefin, allyl glycidyl ether
Should, their reaction can be utilized to prepare the silicone oil containing chain alkyl and propyl glycidyl ether base simultaneously.Propyl group in side base
When glycidyl ether ratio is higher, yield is higher, and action effect is preferable, and preparation contains higher propyl glycidyl ether base/long-chain
Alkyl is than the polysiloxanes of side base, and it has simultaneously to inorganic particle filled polyolefin modified system, and lubrication is scattered, surface is smooth
The function such as anti-scratch, development significance are great.
Hydrosilylation occurs under platinum catalysis for long-chain unsaturated olefin, allyl glycidyl ether and containing hydrogen silicone oil
Active different, the reactivity of long-chain unsaturated olefin is higher, reaction speed faster, simply control long-chain unsaturated olefin with
The rate of charge of allyl glycidyl ether is difficult the ratio of chain alkyl and propyl glycidyl ether base in control silicone product
Example, it is of the invention by being first complexed the double bond in the platinum in chloroplatinic acid and long-chain unsaturated olefin, allyl glycidyl ether, and
Platinum is reduced into zeroth order and divalence, such allyl glycidyl ether hydrosilylation activity greatly improves, and long-chain is unsaturated
The reactivity of alkene, allyl glycidyl ether and containing hydrogen silicone oil approaches, and is reacted substantially by rate of charge, by controlling raw material group
Point ratio can reach the purpose of control product structure；It is another excessive using long-chain unsaturated olefin and allyl glycidyl ether
Method, the hydrogen on containing hydrogen silicone oil is set to react complete；On the other hand, by adding antioxidant and strict controlling reaction temperature, urging
The dosage of agent, make modified silicon oil that the tasteless state of water white transparency be presented.
The side base of the present invention controls containing chain alkyl and epoxy based polysiloxane epoxy group with chain alkyl mol ratio
For more than or equal to 1, during for inorganic particle filled improved polyalkene system, epoxy radicals has strong interaction with inorganic particulate,
Chain alkyl and polyolefin interaction are strong, anchorage effect are played between inorganic particulate and polyolefin, avoid makes well
The migration problem existing for common silicone oil, while retain the effects such as the basic lubrication of silicone oil is scattered, light is anti-scratch.
The object of the invention is achieved through the following technical solutions：
A kind of function additive of side base containing chain alkyl and epoxy based polysiloxane, colourless transparent oil liquid, viscosity
For 200~5000cSt, viscosity average molecular weigh is 1.0 × 104~1.0 × 105G/mol, the modification to polyolefin plastics have lubrication
Scattered and anti-scratch effect, its structural formula are：
Wherein n=6,7,8,10,12,14 or 16, x, y, z represent the composition number of three kinds of construction units, x+y+z=respectively
1, and y/x >=1, wherein x=0.017~0.245, y=0.066~0.490, z=0.917~0.265.
The preparation method of function additive of the described side base containing chain alkyl and epoxy based polysiloxane, including following step
Suddenly：
1) long-chain unsaturated olefin, allyl glycidyl ether and isopropyl alcohol solution of chloroplatinic acid are well mixed, are heated to
75 DEG C~85 DEG C, insulation 0.5~1h of activation, obtain chloroplatinic acid monomer complex；Long-chain unsaturated olefin is controlled to be contracted with pi-allyl
The mol ratio of water glycerin ether is 1:1~4, the structural formula of chloroplatinic acid is H2PtCl6·6H2O, matter of the control chloroplatinic acid in system
Amount concentration is 2~10ppm；
2) in chloroplatinic acid monomer complex obtained by step 1), nitrogen is passed through, toluene and antioxidant is added, is warming up to 80 DEG C
~90 DEG C, containing hydrogen silicone oil is added dropwise, continues 3~6h of reaction after dripping, removing low-boiling-point substance is evaporated under reduced pressure at 50~70 DEG C, is not had
Drop improves temperature to 110~120 DEG C after producing, further remove low-boiling-point substance, until terminating during no drop, obtain side base and contain
The function additive of chain alkyl and epoxy based polysiloxane.
Further to realize the object of the invention, it is preferable that the viscosity of the containing hydrogen silicone oil is 110~4230cSt, glues and divides equally
Son amount is 6.5 × 103~8.9 × 104G/mol, its structural formula are：
Wherein a, b represent the composition number of two kinds of construction units, a+b=1, a=0.083~0.735, b=0.917 respectively
~0.265.
Preferably, the structural formula of the long-chain unsaturated olefin is：
CH2=CH (CH2)mCH3
Wherein m=5,6,7,9,11,13 or 15.
Preferably, the dosage of the toluene is the 1~1.5 of long-chain unsaturated olefin and allyl glycidyl ether gross mass
Times.
Preferably, the antioxidant be four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, N,
N'- pairs-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine or β-(3,5- di-tert-butyl-hydroxy phenyls)
The positive octadecanol ester of propionic acid, the dosage of antioxidant are the 0.5% of long-chain unsaturated olefin and allyl glycidyl ether gross mass
~1%.
Preferably, it is Si-H in containing hydrogen silicone oil to control the total mole number of long-chain unsaturated olefin and allyl glycidyl ether
1.1~1.3 times of bond number.
Preferably, the mass percentage concentration of the isopropyl alcohol solution of chloroplatinic acid is 0.5~2%.
Compared with the prior art, the present invention has the advantages that：
(1) present invention is first by the double bond network in the platinum in chloroplatinic acid and long-chain unsaturated olefin, allyl glycidyl ether
Close, the platinum of tetravalence is reduced into zeroth order and divalence with the double bond in long-chain unsaturated olefin and had more by allyl glycidyl ether
High activity, such hydrosilylation activity greatly improve, and containing hydrogen silicone oil and long-chain unsaturated olefin, allyl glycidyl
The reactivity of glycerin ether approaches, and is reacted substantially by rate of charge.
(2) because the polysiloxane molecule structure side base contains a certain proportion of chain alkyl and propylglycidyl simultaneously
Ether group, it is biradical modified polyorganosiloxane, during for inorganic particle filled improved polyalkene system, epoxy radicals and inorganic particulate
With strong interaction, chain alkyl and polyolefin interaction are strong, and anchorage effect is played between inorganic particulate and polyolefin,
Avoid well using migration problem existing for common silicone oil, while it is scattered, bright anti-scratch to retain the basic lubrication of silicone oil
Effect, have and lubricate the function such as scattered, anti-scratch.
Brief description of the drawings
Fig. 1 is infrared spectrogram of the gained side base of embodiment 1 containing dodecyl and epoxy based polysiloxane.
Fig. 2 is the gained side base of embodiment 1 containing dodecyl and epoxy based polysiloxane1H nmr spectrums.
Embodiment
Preferably to support the present invention, the present invention is further illustrated with reference to the accompanying drawings and examples, but this
The embodiment not limited to this of invention.
Antioxidant used in embodiment has four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (trades mark：
Antioxidant 1010), N, N'- it is double-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine (trade mark：Antioxidant
And β-positive octadecanol ester (trade mark of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid 1098)：Antioxidant 1076).
Embodiment 1
Take 5.32g 1- laurylenes (95%), 10.38g allyl glycidyl ethers (99%) and 0.17g 0.5%
H2PtCl6·6H2O aqueous isopropanol is heated to 80 DEG C, insulation activation 1h, obtained in 150ml four-hole boiling flasks after well mixed
To chloroplatinic acid monomer complex；Nitrogen is passed through into flask, 16g toluene and 0.13g antioxidant 1010s is added, is warming up to 85 DEG C,
Dripped in 1h 50g containing hydrogen silicone oils (Shanghai Gui You new materials Co., Ltd, its per 100g containing hydrogen silicone oils in hydrogen matter on Si -- H bond
Son quality (H%) be 0.2, viscosity 620cSt), after continue react 4h, at 60 DEG C be evaporated under reduced pressure removing low-boiling-point substance, do not have
After drop produces, temperature is improved to 117 DEG C and further removes low-boiling-point substance, until terminating to be evaporated under reduced pressure during no drop, cooled down
After obtain colourless transparent oil liquid, contain dodecyl and epoxy based polysiloxane function additive for side base, with Ubbelohde viscosity
Measure to obtain kinematic viscosity (υ25, toluene is solvent) and it is 930cSt, by formulaCalculating must glue respectively
Son amountFor 3.0 × 104g/mol；
Sampling carries out infrared spectrum analysis, as a result such as accompanying drawing 1, it was found from figure, 802cm-1And 1261cm-1There is Si- in place
The characteristic absorption peak of C keys, 1025cm-1And 1080cm-1There is Si-O-Si feature stretching vibration peak, 2963cm in place-1Place goes out
Existing-CH3C-H stretching vibration peaks, while in 1407cm-1There is saturation C-H flexural vibrations peak, 2250cm in place-1And 910cm-1
Place does not have-Si-H flexible and flexural vibrations peak, illustrates that the si-h bond on containing hydrogen silicone oil is reacted completely, alkene indicated above
Propyl glycidyl ether and 1- laurylenes fully react with containing hydrogen silicone oil, become the side base of polysiloxanes；
Its1H nuclear magnetic resoance spectrums such as accompanying drawing 2, in the group hydrogen corresponding to spectrum chart display each peak, corresponding to dodecyl
Peak is j, h and i, and the peak corresponding to propyl glycidyl ether is respectively a, b, c, d, e, f and j ', k Si-CH3On H
Corresponding peak, spectrogram illustrate that allyl glycidyl ether and 1- laurylenes fully become polysiloxanes with containing hydrogen silicone oil reaction
Side base；Propyl glycidyl ether base is represented with the peak area at d peaks in spectrogram, the peak area at i peaks represents dodecyl, calculated
Two group ratios are 2.5:1, close to 3:1 allyl glycidyl ether and 1- laurylene raw material rate of charges, illustrate allyl glycidyl
The reactivity of glycerin ether, 1- laurylenes and containing hydrogen silicone oil approaches, and is reacted substantially by rate of charge, can be by controlling raw material components
Ratio can reach the purpose of control product structure.
Embodiment 2
Take 8.51g 1- hexadecylenes (95%), 22.10g allyl glycidyl ethers (99%) and 0.26g 1%
H2PtCl6·6H2O aqueous isopropanol is heated to 75 DEG C, insulation activation 0.5h in 250ml four-hole boiling flasks after well mixed,
Obtain chloroplatinic acid monomer complex；Nitrogen is passed through into flask, 40g toluene and 0.28g antioxidant 1098 is added, is warming up to 85
DEG C, after 50g containing hydrogen silicone oils (Shanghai Gui You new materials Co., Ltd, H% 0.4, viscosity 1020cSt) are dripped in 1h,
Continue to react 6h, removing low-boiling-point substance is evaporated under reduced pressure at 70 DEG C, after being produced without drop, temperature is improved to 110 DEG C further
Low-boiling-point substance is removed, until terminating to be evaporated under reduced pressure during no drop, colourless transparent oil liquid is obtained after cooling, contains 16 for side base
Alkyl and epoxy based polysiloxane function additive, kinematic viscosity (υ is measured with Ubbelohde viscometer25, toluene is solvent) be
3040cSt, by formulaCalculate viscosity average molecular weigh be 7.0 × 104g/mol。
Embodiment 3
Take 13.29g 1- octadecylenes (95%), 14.99g allyl glycidyl ethers (99%) and 0.04g 1.5%
H2PtCl6·6H2O aqueous isopropanol is heated to 78 DEG C, insulation activation 0.5h in 250ml four-hole boiling flasks after well mixed,
Obtain a kind of chloroplatinic acid monomer complex；Nitrogen is passed through into flask, 34g toluene and 0.20g antioxidant 1076s is added, is warming up to
90 DEG C, 50g containing hydrogen silicone oils (Shanghai Gui You new materials Co., Ltd, H% 0.3, viscosity 764cSt) are dripped in 1h, after
Continue to react 6h, removing low-boiling-point substance is evaporated under reduced pressure at 50 DEG C, after being produced without drop, temperature is improved to 120 DEG C further
Remove low-boiling-point substance, until terminating to be evaporated under reduced pressure during no drop, obtain colourless transparent oil liquid, for side base containing octadecyl with
And epoxy based polysiloxane function additive, measure kinematic viscosity (υ with Ubbelohde viscometer25, toluene is solvent) and it is 1900cSt, press
FormulaCalculate viscosity average molecular weigh be 5.0 × 104g/mol。
Embodiment 4
Take 3.15g 1- octenes (98%), 3.17g allyl glycidyl ethers (99%) and 0.09g 2%H2PtCl6·
6H2O aqueous isopropanol is heated to 82 DEG C, insulation activation 0.5h, obtains chlorine platinum in 150ml four-hole boiling flasks after well mixed
Acid monomers compound；Nitrogen is passed through into flask, 9g toluene and 0.06g antioxidant 1010s is added, is warming up to 80 DEG C, is dripped in 2h
Add 50g containing hydrogen silicone oils (Shanghai Gui You new materials Co., Ltd, H% 0.1, viscosity 4230cSt), after continue react 4h,
Removing low-boiling-point substance is evaporated under reduced pressure at 70 DEG C, after being produced without drop, temperature is improved to 115 DEG C and further removes low-boiling-point substance,
Until terminating to be evaporated under reduced pressure during no drop, colourless transparent oil liquid is obtained after cooling, contains octyl and epoxy for side base
Based polysiloxane function additive, kinematic viscosity (υ is measured with Ubbelohde viscometer25, toluene is solvent) and it is 5000cSt, by formulaCalculate viscosity average molecular weigh be 1.0 × 105g/mol。
Embodiment 5
Take 6.64g 1- decene (95%), 15.57g allyl glycidyl ethers (99%) and 0.17g 1%H2PtCl6·
6H2O aqueous isopropanol is heated to 75 DEG C, insulation activation 1h, obtains chloroplatinic acid in 250ml four-hole boiling flasks after well mixed
Monomer complex；Nitrogen is passed through into flask, 33g toluene and 0.11g antioxidant 1098 is added, is warming up to 80 DEG C, is dripped in 1h
Add 50g containing hydrogen silicone oils (Shanghai Gui You new materials Co., Ltd, H% 0.3, viscosity 110cSt), after continue react 5h,
Removing low-boiling-point substance is evaporated under reduced pressure at 70 DEG C, after being produced without drop, temperature is improved to 120 DEG C and further removes low-boiling-point substance, directly
Terminate to be evaporated under reduced pressure during to no drop, colourless transparent oil liquid is obtained after cooling, contain decyl and epoxy radicals for side base
Polysiloxanes function additive, kinematic viscosity (υ is measured with Ubbelohde viscometer25, toluene is solvent) and it is 200cSt, by formulaCalculate viscosity average molecular weigh be 1.0 × 104g/mol。
Embodiment 6
Take 23.03g 1- octadecylenes (95%), 19.99g allyl glycidyl ethers (99%) and 0.16g 1.5%
H2PtCl6·6H2O aqueous isopropanol is heated to 75 DEG C, insulation activation 1h, obtained in 250ml four-hole boiling flasks after well mixed
To chloroplatinic acid monomer complex；Nitrogen is passed through into flask, 60g toluene and 0.26g antioxidant 1098 is added, is warming up to 85 DEG C,
50g containing hydrogen silicone oils (Shanghai Gui You new materials Co., Ltd, H% 0.4, viscosity 1150cSt) are dripped in 1h, it is rear to continue
3h is reacted, removing low-boiling-point substance is evaporated under reduced pressure at 70 DEG C, after being produced without drop, temperature is improved to 120 DEG C of further removings
Low-boiling-point substance, until terminating to be evaporated under reduced pressure during no drop, colourless transparent oil liquid is obtained after cooling, contain octadecyl for side base
And epoxy based polysiloxane function additive, measure kinematic viscosity (υ with Ubbelohde viscometer25, toluene is solvent) and 5000cSt, is pressed
FormulaCalculate viscosity average molecular weigh be 1.0 × 105g/mol。
Application Example
Using function additive of the side base made from above-described embodiment containing chain alkyl and epoxy based polysiloxane, to 30%
Talcum powder (Guangzhou Rong Yue industrial chemicals Co., Ltd, 1250 mesh) filling polypropylene (Sinopec Central Plains Chemical Co., Ltd.,
PPH-M16) it is lubricated scattered, anti-scratch modification.Using double screw extruder, (model LTE26/40, German LabTech is public
Department) first extrusion obtain pellet, then using compression molding instrument carry out tabletting sample preparation；Each zone temperature of double-screw extruding machine barrel
For：First 160 DEG C of area, the second 170 DEG C of area, the 3rd 180 DEG C of area, the 4th 190 DEG C of area, the 5th 190 DEG C of area, the 6th 190 DEG C of area, the
Seven 190 DEG C of areas, 190 DEG C of Section Eight, the 9th 185 DEG C of area, 180 DEG C of head, engine speed 280r/min.Tablet forming technique condition is：
The 210 DEG C first iron mould 5min of preheating, 4min is cold-pressed after suppressing 4min again.Side base is containing length used by Application Example 1~3
Alkyl group and the function additive species of epoxy based polysiloxane and each raw material proportioning row such as table 1.
To be not added with function additive of the side base containing chain alkyl and epoxy based polysiloxane, by 30% talc poly- third
Alkene is comparative example 1.
Helped with conventional hydroxy silicon oil (Rong Li Chemical Co., Ltd.s, the trade mark 107, viscosity are 250~300cSt) for function
Agent, as a comparison case 2 are modified to the polypropylene of 30% talc, its raw material proportioning row such as table 1.
Surface is carried out using the electronic ten strokes lattice instrument of German ERICHSEN 430P-1 and draws lattice, draws the quasi- reference of case marker
GMW14688 standards, rubbing head is scraped using 0.5mm, with 1000mm/min speed on plastic plate under 5N pressure effect,
Scrape 20 stripe pitch 4mm, length 40mm scratch, a direction draw plastic plate being rotated by 90 ° after lattice draws lattice again；By
Plastic plate after ten stroke lattice is using Dutch TQC GL0010 vancometers to gesticulating the change (△ L) of glossiness (L) before and after lattice
To judge frosting Scratch Resistance energy, the smaller explanation glossiness change of △ L values is smaller, i.e., Scratch Resistance can be better.
The test condition of counter balance torque：Tester is Hakke banburying instrument, 190 DEG C, rotating speed 60r/min of temperature, during test
Between 6min.Melt flow rate (MFR) (MFR) is determined by GB/T 3682-2000.
The raw material proportioning of the Application Example 1~3 of table 1 and comparative example 1~2
The scraping and wiping resistance performance and counter balance torque of Application Example 1~3 and comparative example 1~2, melt flow rate (MFR) (MFR, 190
DEG C, 21.6kg) such as table 2.
As shown in Table 2, with not plus compared with the comparative example 1 of function additive, the counter balance torque of each Application Example, △ L values are equal
Reduce；In addition, the counter balance torque of each Application Example, △ L values illustrate that side base contains chain alkyl and ring also below comparative example 2
Epoxide polysiloxanes has lubrication peptizaiton and Scratch Resistance to polypropylene, and is better than conventional lubricant hydroxy silicon oil.Adopt
Minimum, the △ with side base long-chain containing dodecyl and the counter balance torque (7.57N*m) of the Application Example 1 of epoxy based polysiloxane
L (1.39) is minimum, and the counter balance torque than comparative example 1 reduces 27%, △ L and reduces 28%, and the counter balance torque than comparative example 2 drops
Low 25%, △ L reduce 19%；Melt flow rate (MFR) (2.96g/10min) highest, than the melt flow rate (MFR) of comparative example 1
(1.35g/10min) improves 120%, and the melt flow rate (MFR) (1.96g/10min) than comparative example 2 improves 51%.To sum up
Described, side base of the present invention is applied in the polyacrylic modification of high polymer material containing chain alkyl and epoxy based polysiloxane to be had
The effect such as scattered, anti-scratch is lubricated, is a kind of function additive of good performance.
The lubrication of the Application Example 1~3 of table 2 and comparative example 1~2 is disperseed and anti-scratch results of property
Claims (8)
1. function additive of a kind of side base containing chain alkyl and epoxy based polysiloxane, it is characterised in that be colorless transparent oil
Shape liquid, viscosity are 200~5000cSt, and viscosity average molecular weigh is 1.0 × 104~1.0 × 105G/mol, polyolefin plastics is changed
Property have lubrication scattered and anti-scratch effect, its structural formula are：
Wherein n=6,7,8,10,12,14 or 16, x, y, z represent the composition number of three kinds of construction units respectively, x+y+z=1, and
Y/x >=1, wherein x=0.017~0.245, y=0.066~0.490, z=0.917~0.265.
2. the preparation method of function additive of the side base containing chain alkyl and epoxy based polysiloxane described in claim 1, its
It is characterised by comprising the following steps：
1) long-chain unsaturated olefin, allyl glycidyl ether and isopropyl alcohol solution of chloroplatinic acid are well mixed, are heated to 75 DEG C
~85 DEG C, insulation 0.5~1h of activation, obtain chloroplatinic acid monomer complex；Control long-chain unsaturated olefin and allyl glycidyl sweet
The mol ratio of oily ether is 1:1~4, the structural formula of chloroplatinic acid is H2PtCl6·6H2O, quality of the control chloroplatinic acid in system are dense
Spend for 2~10ppm；
2) in chloroplatinic acid monomer complex obtained by step 1), nitrogen is passed through, toluene and antioxidant is added, is warming up to 80 DEG C~90
DEG C, containing hydrogen silicone oil is added dropwise, continues 3~6h of reaction after dripping, removing low-boiling-point substance is evaporated under reduced pressure at 50~70 DEG C, without drop
Temperature is improved after generation to 110~120 DEG C, low-boiling-point substance is further removed, until terminating during no drop, obtains side base and contain long-chain
The function additive of alkyl and epoxy based polysiloxane.
3. the preparation side of function additive of the side base according to claim 2 containing chain alkyl and epoxy based polysiloxane
Method, it is characterised in that the viscosity of the containing hydrogen silicone oil is 110~4230cSt, and viscosity average molecular weigh is 6.5 × 103~8.9 × 104g/
Mol, its structural formula are：
Wherein a, b represents the composition number of two kinds of construction units respectively, a+b=1, a=0.083~0.735, b=0.917~
0.265。
4. the preparation side of function additive of the side base according to claim 2 containing chain alkyl and epoxy based polysiloxane
Method, it is characterised in that the structural formula of the long-chain unsaturated olefin is：
CH2-CH(CH2)mCH3
Wherein m=5,6,7,9,11,13 or 15.
5. the preparation side of function additive of the side base according to claim 2 containing chain alkyl and epoxy based polysiloxane
Method, it is characterised in that the dosage of the toluene is the 1~1.5 of long-chain unsaturated olefin and allyl glycidyl ether gross mass
Times.
6. the preparation side of function additive of the side base according to claim 2 containing chain alkyl and epoxy based polysiloxane
Method, it is characterised in that：The antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, N, N'-
Double-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine or β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid
Positive octadecanol ester, the dosage of antioxidant for long-chain unsaturated olefin and allyl glycidyl ether gross mass 0.5%~
1%.
7. the preparation side of function additive of the side base according to claim 2 containing chain alkyl and epoxy based polysiloxane
Method, it is characterised in that：It is Si-H in containing hydrogen silicone oil to control the total mole number of long-chain unsaturated olefin and allyl glycidyl ether
1.1~1.3 times of bond number.
8. the preparation side of function additive of the side base according to claim 2 containing chain alkyl and epoxy based polysiloxane
Method, it is characterised in that：The mass percentage concentration of the isopropyl alcohol solution of chloroplatinic acid is 0.5~2%.
Priority Applications (1)
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| CN111282599A (en) * | 2020-03-25 | 2020-06-16 | 万华化学集团股份有限公司 | Preparation method and application of supported platinum catalyst |
| CN111394053A (en) * | 2020-03-03 | 2020-07-10 | 华南理工大学 | Non-flowing underfill with welding assisting function and preparation method thereof |
| CN113666886A (en) * | 2021-08-26 | 2021-11-19 | 诸暨华海氨纶有限公司 | Antibacterial spandex fiber for diaper and preparation method thereof |
| CN114855455A (en) * | 2022-04-27 | 2022-08-05 | 浙江海利得新材料股份有限公司 | Anti-wicking composition, spinning oil, anti-wicking yarn and preparation method thereof |
| CN115717335A (en) * | 2022-11-28 | 2023-02-28 | 浙江理工大学桐乡研究院有限公司 | Moisture-absorbing and sweat-releasing finishing agent for cotton and preparation method thereof |
| CN115991902A (en) * | 2023-02-09 | 2023-04-21 | 浙江汪洋高分子材料有限公司 | High-gloss scratch-resistant modified polyolefin material and preparation method thereof |
| CN116023666A (en) * | 2023-02-01 | 2023-04-28 | 成都思立可科技有限公司 | Crosslinking agent, silica gel-like TPE and preparation method thereof |
| CN116804086A (en) * | 2023-08-25 | 2023-09-26 | 成都思立可科技有限公司 | Long-chain alkyl-polar group co-modified polysiloxane and preparation method thereof |
| CN116919839A (en) * | 2023-09-04 | 2023-10-24 | 广州市胜梅化妆品有限公司 | Even-brightness stable synergistic component and collagen multiple peptide combined component prepared from same |
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| TWI669315B (en) * | 2018-02-07 | 2019-08-21 | 奇美實業股份有限公司 | Modified polymethylhydrosiloxane, modified high cis conjugated diene polymer and manufacturing method thereof, rubber composition and tire |
| CN111394053A (en) * | 2020-03-03 | 2020-07-10 | 华南理工大学 | Non-flowing underfill with welding assisting function and preparation method thereof |
| CN111394053B (en) * | 2020-03-03 | 2021-10-26 | 华南理工大学 | Non-flowing underfill with welding assisting function and preparation method thereof |
| CN111282599A (en) * | 2020-03-25 | 2020-06-16 | 万华化学集团股份有限公司 | Preparation method and application of supported platinum catalyst |
| CN111282599B (en) * | 2020-03-25 | 2022-07-12 | 万华化学集团股份有限公司 | Preparation method and application of supported platinum catalyst |
| CN113666886A (en) * | 2021-08-26 | 2021-11-19 | 诸暨华海氨纶有限公司 | Antibacterial spandex fiber for diaper and preparation method thereof |
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| CN114855455A (en) * | 2022-04-27 | 2022-08-05 | 浙江海利得新材料股份有限公司 | Anti-wicking composition, spinning oil, anti-wicking yarn and preparation method thereof |
| CN115717335A (en) * | 2022-11-28 | 2023-02-28 | 浙江理工大学桐乡研究院有限公司 | Moisture-absorbing and sweat-releasing finishing agent for cotton and preparation method thereof |
| CN116023666A (en) * | 2023-02-01 | 2023-04-28 | 成都思立可科技有限公司 | Crosslinking agent, silica gel-like TPE and preparation method thereof |
| CN115991902A (en) * | 2023-02-09 | 2023-04-21 | 浙江汪洋高分子材料有限公司 | High-gloss scratch-resistant modified polyolefin material and preparation method thereof |
| CN115991902B (en) * | 2023-02-09 | 2024-05-31 | 浙江汪洋高分子材料有限公司 | High-gloss scratch-resistant modified polyolefin material and preparation method thereof |
| CN116804086A (en) * | 2023-08-25 | 2023-09-26 | 成都思立可科技有限公司 | Long-chain alkyl-polar group co-modified polysiloxane and preparation method thereof |
| CN116804086B (en) * | 2023-08-25 | 2023-11-07 | 成都思立可科技有限公司 | Long-chain alkyl-polar group co-modified polysiloxane and preparation method thereof |
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| CN117186550B (en) * | 2023-10-25 | 2024-04-05 | 广东昊威新材料科技有限公司 | Anti-aging PP flame-retardant plate and preparation method thereof |
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