CN106977728A - Makrolon graft copolymer and preparation method thereof - Google Patents
Makrolon graft copolymer and preparation method thereof Download PDFInfo
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- CN106977728A CN106977728A CN201710278224.2A CN201710278224A CN106977728A CN 106977728 A CN106977728 A CN 106977728A CN 201710278224 A CN201710278224 A CN 201710278224A CN 106977728 A CN106977728 A CN 106977728A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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Abstract
The invention discloses makrolon graft copolymer and preparation method thereof.The preparation method its by represented by the makrolon containing double bond represented by formula I and formula II hydrogen containing siloxane carry out Si―H addition reaction obtained by；Wherein, R7、R8、R9For alkane or phenyl ring, R0、R1、R2、R3、R4For alkyl or aromatic radical, R5、R6For hydrogen, alkyl or aromatic radical；M is 1~70 positive integer, x and y sums are 20~70 positive integer.The preparation method of the present invention has product structure controllable, and preferably, resulting product impact strength is preferable for homogeneity of product.
Description
Technical field
The present invention relates to the technical field of engineering plastics, in particular to makrolon graft copolymer and its preparation
Method.
Background technology
Makrolon (PC) is one of five large-engineering plastics, and it has high strength, high-fire resistance, good electrical insulating property
With numerous excellent properties such as dimensional stability, thus can be widely applied to machinery, aviation, traffic, optics, electronic apparatus, agricultural,
The multiple fields such as weaving, medical treatment.But, exposed day by day goes out the deficiency of itself to PC in actual applications, shows as PC at low temperature
Notch impact strength it is poor, seriously limit its application under severe cold area or low temperature environment, PC fire-retardant rank (UL-
Use requirement of the high flame resistance product in some fields, and PC easy sticking to moulds in injection moulding process can not 94V-2) be met,
Release property is poor, it is impossible to meet manufacture requirement of large-scale thin wall parts etc..Overcome PC above-mentioned deficiency, be to solve PC practical applications to ask
The fundamental way of topic, is also the purport place of this work.Polysiloxanes (such as PDMS) have low-temperature flexibility, low-surface-energy and
The performance characteristics such as fire-retardant, in view of its complementation with PC performances, it is desirable to by its copolymer with makrolon, improve itself and PC bases
While compatability, its performance characteristics, comprehensive low-temperature flexibility, release property and the anti-flammability for improving PC etc. are played.
In the prior art, generally it is utilized in makrolon building-up process and adds the poly dimethyl silicon with reactive group
Oxygen alkane monomer, such as phenolic hydroxyl group realizes the copolymerization in makrolon and dimethyl silicone polymer.Its course of reaction is as follows：
The course of reaction is currently the synthetic method being most widely used at present, and its bridging mode is end group overseas Chinese federation, synthesis
During must use phosgene, it is necessary to be solwution method synthesis, and building-up process technological requirement is harsh, obtained polymer architecture is past
Past uncontrollable, homogeneity of product is bad, the processing performance in influence later stage.
The content of the invention
In view of this, one aspect of the present invention is to provide a kind of product knot of the preparation method of makrolon graft copolymer
Structure is controllable, and homogeneity of product is preferably, and resulting product impact strength is preferable.
A kind of preparation method of makrolon graft copolymer, its makrolon containing double bond and formula II represented by formula I
Represented hydrogen containing siloxane is carried out obtained by Si―H addition reaction；
Wherein, R7、R8、R9For alkane or phenyl ring, R0、R1、R2、R3、R4For alkyl or aromatic radical, R5、R6For hydrogen, alkyl or
Aromatic radical；M is 1~70 positive integer, x and y sums are 20~70 positive integer.
Further, the R7For
Further, the R8ForN is 1~20 positive integer.
Further, the mol ratio of the makrolon containing double bond and hydrogen containing siloxane is 1：(0.1~10).
Further, the mol ratio of the makrolon containing double bond and hydrogen containing siloxane is 1：1.
Further, the hydrosilylation is carried out in a solvent, and the solvent is toluene, dimethylbenzene, tetrahydrofuran
It is middle a kind of or at least two kinds.
Further, the temperature of the hydrosilylation carried out in the solvent is 40~100 DEG C.
Further, the catalyst of the hydrosilylation is silica gel load platinum complex and/or chloroplatinic acid.
Further in the silicon hydrogen is additionally added alkene in reacting.
Another aspect of the present invention is to provide a kind of makrolon graft copolymer, and the makrolon graft copolymer has
Preferable impact strength.
A kind of makrolon graft copolymer, as the scion grafting polymer obtained by above-mentioned preparation method.
The preparation method of the makrolon graft copolymer of the present invention, due to makrolon containing double bond and hydrogeneous poly- silica
Alkane passes through obtained by hydrosilylation so that product structure is controllable, and homogeneity of product is preferably, and resulting product impact is strong
Degree is preferable.
Embodiment
Unless otherwise defined, all technologies used herein and scientific terminology have and the common skill of art of the present invention
The identical implication that art personnel are generally understood that.When there is contradiction, the definition in this specification is defined.
Term as used herein：
" by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing "
Or its any other deformation, it is intended that cover including for non-exclusionism.For example, composition, step, method comprising listed elements,
Product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or such a composition, step
Suddenly, method, product or the intrinsic key element of device.
Conjunction " by ... constitute " exclude any key element do not pointed out, step or component.If be used in claim,
This phrase will make claim be closed, it is not included the material in addition to materials of those descriptions, but relative
Except customary impurities.When phrase " by ... constitute " be rather than immediately following theme in the clause that appears in claim main body after
When, it is only limited to the key element described in the clause；Other key elements be not excluded as the overall claim it
Outside.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value is limited, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open
Scope " when 1~5 ", described scope should be interpreted as including scope " 1~4 ", " 1~3 ", " 1~2 ", " 1~2 and 4~
5 ", " 1~3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
" mass parts " refer to the basic measurement unit for the mass ratio relation for representing multiple components, and 1 part can represent arbitrary list
Position quality, can such as be expressed as 1g, may also indicate that 2.689g etc..If we say that the mass parts of component A are a parts, the matter of B component
It is b parts to measure part, then it represents that the quality of component A and the mass ratio a of B component：b.Or, the quality for representing component A is aK, B groups
The quality divided is bK (K is Arbitrary Digit, represents multiplying factor).It can not misread, and unlike mass fraction, all components
Mass parts sum be not limited to 100 parts of limitation.
"and/or" is used to represent that one of illustrated situation or both may to occur, for example, A and/or B includes (A
And B) and (A or B)；
In addition, the indefinite article " one kind " and " one " before key element of the present invention or component are to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
The preparation method of makrolon graft copolymer of the present invention, its makrolon containing double bond and formula represented by formula I
Hydrogen containing siloxane represented by II is carried out obtained by Si―H addition reaction；
Wherein, R7、R8、R9For alkane or phenyl ring, R0、R1、R2、R3、R4For alkyl or aromatic radical, R5、R6For hydrogen, alkyl or
Aromatic radical；M is 1~70 positive integer, x and y sums are 20~70 positive integer.
In above-mentioned formula I, R7、R8、R9It is able to can also be differed with identical.Makrolon can for fatty poly-ester carbonate or
Aromatic copolycarbonate.Can be bisphenol-a polycarbonate, i.e. R for aromatic copolycarbonate7ForThe group being connected with double bond is preferably aromatic hydrocarbon, such as R8For
N is 1~20 positive integer, such as n is 1,2,3,4.
In above-mentioned formula II, R0、R1、R2、R3、R4Can be with identical or differ, R5、R6One can be used as with identical or differ
Plant embodiment, R5、R6For the tert-butyl group, R0、R1、R2、R3、R4For methyl, i.e. 202 containing hydrogen silicone oils, it is.Implement as another
Mode, containing hydrogen silicone oil is phenyl hydrogen-containing silicon oil, specifically, for example R5、R6For-H, R1、R2、R3、R4For methyl or phenyl, R0For
Phenyl, is referred to such as periodical literature " preparation of LED methyl and phenyl hydrogen-containing silicon oil for packaging, Cheng Lin is chanted, bonding ", or as in
Phenyl hydrogen-containing silicon oil prepared by the method described in state patent CN101974157A.
It is the referring to property of reaction mol ratio of makrolon containing double bond and hydrogen containing siloxane 1：(0.1~10), for example
1：0.1、1：0.2、1：0.5、1：1、1：3、1：5、1：8、1：9、1：9.5 or 1：10 etc..Preferably, makrolon containing double bond and
The molar ratio 1 of hydrogen containing siloxane：1.
According to actual needs, can be more than in effective molar ratio range, by using the first of different molecular weight and hydrogen content
Base containing hydrogen silicone oil effectively adjusts the silicone content of final product.
In order to improve the higher yield of reaction and accelerate reaction speed, hydrosilylation should can enter in a solvent
OK, the solvent is one kind in toluene, dimethylbenzene, tetrahydrofuran or at least two kinds.Certainly, can also be using other solvents.
In order to further improve the higher yield of reaction and accelerate reaction speed, it can enter under conditions of catalyst
OK.Catalyst can include Speier catalyst, Karstedt catalyst, platinum complex catalyst, and preferably platinum complex is urged
Agent.Platinum complex catalyst, is such as included in platinum -ol complex, platinum-vinyl siloxane complex, platinum-olefin complex
A kind of and its any combination.Here, the alcoholic solution of chloroplatinic acid can for chloroplatinic acid be dissolved in such as ethanol, methanol, isopropanol,
Octanol etc..The collocation method of chloroplatinic acid isopropanol can be specially：By 3g H2PtCl·6H2O is dissolved in 100ml anhydrous isopropyl alcohols,
(such as room temperature) is sufficiently stirred at a certain temperature, is made its complete molten rear standing a period of time, is both obtained product, be finally orange colour
Molten, its chemical equation is H2PtCl·6H2O+(CH3)2CHOH→H2PtCl4(CH3)2CO+2HCl+6H2O.Chloroplatinic acid octanol
Collocation method is specially：H2PtCl·6H2O and 2-ethylhexanol (specific one kind of octanol) are 1：The reactant mixture of 7 generations,
Water is removed under reacting 4h at 70 DEG C under 250mm Hg pressure, and being then depressurized to 2mmHg removes unreacted alcohol, is cooled to room
Temperature, filtering, filtrate is sticky light brown liquid, and as platinum containing amount is 21% (weight), chloride 8.3% platinum catalyst.This
In, platinum-vinyl siloxane complex refers to that chloroplatinic acid is obtained with vinyl silicone compounds complex reaction, vinyl silica
Hydride compounds can for tetramethyl divinyl disiloxane (vinyl double seal head), dimethoxy-methyl vinylsiloxane,
T etram-ethyltetravinylcyclotetrasiloxane etc..So that vinylsiloxane is tetramethyl divinyl disiloxane as an example, platinum-ethene
The preparation method of radical siloxane complex can be：With reflux condenser, in the reaction bulb of thermometer, add 32g chloroplatinic acids and
210g tetramethyl divinyl disiloxanes, in normal pressure and 120 DEG C of backflow 1h, filter off black precipitate (platinum black) and will be shallow after cooling
The anti-handy distillation of grey acid solution is washed to neutral (removing chloride acidic by-products) and then adds anhydrous CaCl2 dryings,
Filter out CaCl2Afterwards, the platinum-vinyl siloxane for obtaining platiniferous 2.2% (mass fraction) and chloride 0.43% (mass fraction) is matched somebody with somebody
Compound.Or so that vinylsiloxane is t etram-ethyltetravinylcyclotetrasiloxane as an example, platinum-vinyl siloxane complex
Preparation method can be 6g chloroplatinic acids, 180ml absolute ethyl alcohols and 6g NaCO3, 300g t etram-ethyltetravinylcyclotetrasiloxanes are 80
Flow back 2h at DEG C, washes (can not wash) dry filter product.Here, platinum-carboxylate complex refers to that chloroplatinic acid enters with carboxylate
Product obtained by row complex reaction.Carboxylate can be the aliphatic carboxylic acid esterss such as ethyl acetate, Ethyl formate, or with O-phthalic
The aromatic carboxylic acid esters of diethyl phthalate etc..By taking carboxylate as an example, the preparation method of platinum-carboxylate complex is：With backflow
In the 500ml there-necked flasks of condenser temperature meter, 1g chloroplatinic acids and 200ml absolute ethyl alcohols are added, leads to N2Under (drying), 80 are warming up to
DEG C backflow 2h, is then cooled to 40 DEG C, decompression steams ethanol, obtains clear yellow viscous thing, through chloroform and after removing solvent, just
Solid product (extracting 10 times or so), adds 50g diethyl phthalate dissolved solid things, and filtering off solid slag makes to obtain adjacent benzene two
The co-ordination complex catalyst of formic acid diethylester.Except this, platinum-non-metal complexes can also be platinum-tetrahydrofuran complex.Platinum-
The preparation method of tetrahydrofuran complex can be：In the reaction bulb with reflux condenser and thermometer, 1g chloroplatinic acids are added
And 200ml tetrahydrofurans, in logical N2In the case of flow back 1h, add Na after cooling2SO4Dry, filter off solid scoriform thing, both
Tetrahydrofuran co-ordination complex solution.It is the referring to property of content of platinum 3000~10000ppm in this platinum complex catalyst.
In the present invention, catalyst can be silica gel load platinum complex and/or chloroplatinic acid.
The temperature of the hydrosilylation carried out in a solvent be 40~100 DEG C, such as 40 DEG C, 45 DEG C, 50 DEG C, 60 DEG C,
70 DEG C, 90 DEG C, 95 DEG C or 100 DEG C etc., preferably 50 DEG C.
For silicon hydrogen group remaining in elimination reaction system, alkene can be added.Alkene can include ethene or oneself
Alkene etc..
Makrolon graft copolymer of the present invention, as the scion grafting polymer obtained by above-mentioned preparation method.
As a kind of preferred embodiment, makrolon graft copolymer has following structural formula
Its prepare equation be：
Its brittle fracture rate of the 30C notch shocks of the makrolon graft copolymer obtained by the preparation method is less than
50%.
Do not address part above and be applied to prior art.
Embodiment 1
100g makrolon A1 are taken, the hydrogeneous polydimethylsiloxane compound B1 of 5g (x+y=39 in B1) are added, four are added
In hydrogen furans, 50C is warming up to, is stirred, after reacting six hours, cooling adds methanol, it is that PC-PDMS is total to obtain white precipitate
Polymers.
It is Mw=20000 that GPC, which measures gained molecular weight of copolymer,.Elementary analysis obtains polydimethyl siloxane content
4.3%.
The performance of gained copolymer：
Room temperature notch impact strength (ASTM D638)：729J/M, brittle fracture rate 0%
- 30C notch impact strengths (ASTM D638)：609J/M, brittle fracture rate 0%
3mm colour tables transmitance (ASTM 1003) T%=89%, mist degree：Haze=1.3%
Embodiment 2
100g makrolon A1 are taken, the hydrogeneous polydimethylsiloxane compound B2 (x+y=47) of 5g are added, tetrahydrochysene furan is added
In muttering, 50C is warming up to, is stirred, after reacting six hours, cooling adds methanol, it is PC-PDMS copolymers to obtain white precipitate.
It is Mw=22000 that GPC, which measures gained molecular weight of copolymer,.Elementary analysis obtains polydimethyl siloxane content
4.3%.
The performance of gained copolymer：
Room temperature notch impact strength (ASTM D638):774J/M, brittle fracture rate 0%
- 30C notch impact strengths (ASTM D638):617J/M, brittle fracture rate 0%
3mm colour tables transmitance (ASTM 1003) T%=89%, mist degree：Haze=1.3%
Embodiment 3
100g makrolon A1 are taken, the hydrogeneous polydimethylsiloxane compound B2 (x+y=47) of 8g are added, tetrahydrochysene furan is added
In muttering, 50C is warming up to, is stirred, after reacting six hours, cooling adds methanol, it is PC-PDMS copolymers to obtain white precipitate.
It is Mw=23000 that GPC, which measures gained molecular weight of copolymer,.Elementary analysis obtains polydimethyl siloxane content
6.6%.
The performance of gained copolymer：
Room temperature notch impact strength (ASTM D638):749J/M, brittle fracture rate 0%
- 30C notch impact strengths (ASTM D638):693/M, brittle fracture rate 0%
3mm colour tables transmitance (ASTM 1003) T%=89%, mist degree：Haze=1.3%.
Because the number range of each technological parameter involved in the present invention can not possibly all embody in the above-described embodiments,
As long as but those skilled in the art's envisioned any numerical value fallen into the above-mentioned number range completely can implement this
Invention, also includes any combination of occurrence in the range of some numerical value certainly.Herein, for the consideration of length, eliminate to
Go out the embodiment of occurrence in certain one or more of number range, this disclosure for being not to be construed as technical scheme is not filled
Point.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, concrete mode selection of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., fall the protection in the present invention
In the range of.
Claims (10)
1. a kind of preparation method of makrolon graft copolymer, it is characterised in that its poly- carbonic acid containing double bond represented by formula I
Hydrogen containing siloxane represented by ester and formula II is carried out obtained by Si―H addition reaction；
Wherein, R7、R8、R9For alkane or phenyl ring, R0、R1、R2、R3、R4For alkyl or aromatic radical, R5、R6For hydrogen, alkyl or fragrance
Base；M is 1~70 positive integer, x and y sums are 20~70 positive integer.
2. preparation method according to claim 1, it is characterised in that the R7For
3. preparation method according to claim 1, it is characterised in that the R8ForN is 1
~20 positive integer.
4. preparation method according to claim 1, it is characterised in that the makrolon containing double bond and hydrogen containing siloxane
Mol ratio be 1：(0.1~10).
5. preparation method according to claim 4, it is characterised in that the makrolon containing double bond and hydrogen containing siloxane
Mol ratio be 1：1.
6. preparation method according to claim 1, it is characterised in that the hydrosilylation is carried out in a solvent, institute
It is one kind in toluene, dimethylbenzene, tetrahydrofuran or at least two kinds to state solvent.
7. preparation method according to claim 6, it is characterised in that the hydrosilylation carried out in the solvent
Temperature is 40~100 DEG C.
8. preparation method according to claim 1, it is characterised in that the catalyst of the hydrosilylation is negative for silica gel
Carry platinum complex and/or chloroplatinic acid.
9. preparation method according to claim 1, it is characterised in that be additionally added alkene in the silicon hydrogen reaction.
10. a kind of makrolon graft copolymer, it is characterised in that as the preparation method described in claim 1~9 any one
Obtained scion grafting polymer.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000044668A (en) * | 1998-07-30 | 2000-02-15 | Idemitsu Kosan Co Ltd | Crosslinked polycarbonate resin composition and absorbent and column packing material using the same |
| CN102942689A (en) * | 2007-05-08 | 2013-02-27 | 出光兴产株式会社 | Polycarbonate polymer |
-
2017
- 2017-04-25 CN CN201710278224.2A patent/CN106977728A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000044668A (en) * | 1998-07-30 | 2000-02-15 | Idemitsu Kosan Co Ltd | Crosslinked polycarbonate resin composition and absorbent and column packing material using the same |
| CN102942689A (en) * | 2007-05-08 | 2013-02-27 | 出光兴产株式会社 | Polycarbonate polymer |
Non-Patent Citations (2)
| Title |
|---|
| 冯新德，等: "《高分子辞典》", 30 June 1998, 中国石化出版社 * |
| 王少辉: ""改性硅油的合成及有机硅/聚碳酸酯共聚物的制备"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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Application publication date: 20170725 |