CN101798464A - Composition for preparing organic silicon elastomer, organic silicon elastomer and preparation method and application thereof - Google Patents
Composition for preparing organic silicon elastomer, organic silicon elastomer and preparation method and application thereof Download PDFInfo
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- CN101798464A CN101798464A CN200910208710A CN200910208710A CN101798464A CN 101798464 A CN101798464 A CN 101798464A CN 200910208710 A CN200910208710 A CN 200910208710A CN 200910208710 A CN200910208710 A CN 200910208710A CN 101798464 A CN101798464 A CN 101798464A
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Abstract
The invention discloses a composition for preparing organic silicon elastomer, which contains polymer A and compound B, wherein the polymer A is silicones polymer containing at least two carboxyl groups, the compound B contains at least two aziridine rings, and the mol ratio of the carboxyl groups of the polymer A to the aziridine rings of the compound B is 1:0.2-10. The invention further discloses a method for preparing organic silicon elastomers by using the composition, and an organic silicon elastomer and application thereof.
Description
Technical field
The present invention relates to a kind of composition that is used to prepare silicone elastomer, and a kind of silicone elastomer and its production and application.
Background technology
Traditional organosilicon curing mainly comprises condensed type and silicon hydrogen add-on type, and wherein condensed type mainly comprises the depickling type, takes off the oxime type, dealcoholizing-type, takes off the amine type, takes off acid amide type, takes off hydroxylamine type and take off acetone type etc.All there is some defective (Feng Shengyu etc. write, organosilicon macromolecule and application thereof, P116～152) in above-mentioned organosilicon curing:
1, the condensed type organic silicon curing all can discharge in solidify reaction process for small molecules volatile organic compoundss (VOC) such as alcohol, acid, acetone and amine, and is unfriendly to environment.
2, the condensed type organic silicon curing need could react under the certain humidity environment, therefore, it is bigger that the curing speed of this method is influenced by ambient moisture, and solidification process is for from outward appearance to inner essence, slow down with the bondline thickness increase, exist completely solidified slow, the top layer quick solidifying, deep layer is solidified slow or deep layer solidified problem not.
3, silicon hydrogen add-on type organosilicon curing solidifies at normal temperatures, needs to add heavy metal catalyst, as complex compound, Karstedt catalyzer or Speier ' the s catalyzer etc. of Pt or Pd.These heavy metal catalyst contaminate environment, cost an arm and a leg, and as easy as rolling off a log " poisoning ", because this type of catalyzer contacts the organism of elements such as containing N, P and S in use, the organism that contains the alkynyl unsaturated link(age), and very easily poison during the ionic compound of heavy metals such as Sn, Pb, Hg, Bi and As.
4, in the silicon hydrogen add-on type organosilicon solidification process,, cause security incident easily because the silicon hydride instability easily discharges inflammable and explosive hydrogen.
Because existing machine has the silicon curing to have above-mentioned defective, a kind of new better novel organosilicon curing of environmental protection, low cost, solidification effect of the demand of demanding urgently.
Summary of the invention
Technical problem to be solved by this invention is easily to discharge volatile organic compounds and maybe need use heavy metal catalyst in order to overcome existing silicoorganic compound curing, or the difficult defective of completely solidified, and a kind of the problems referred to above of avoiding are provided, and the composition that is used to prepare silicone elastomer of the silicone elastomer of availability excellence, and a kind of silicone elastomer and its production and application.
For solving the problems of the technologies described above, the inventor gropes through a large amount of experiments, the final discovery, with aziridines compound as linking agent or chainextender, be cured reaction with the silicone oil compound that has carboxyl, not only avoided the generation of volatile organic compounds, and the use of heavy metal catalyst, and completely solidified is fast, solidification effect is good, and curing speed is not subjected to ambient moisture and catalysts influence, also unexpected the discovery, compare with the silicone elastomer that traditional method makes, silicone elastomer obtained by this method has the excellent comprehensive performance, cohesiveness especially, and apparent transparent.
The composition that is used to prepare silicone elastomer of the present invention contains: polymer A and compd B, described polymer A are the silicone oil polymkeric substance that contains at least two carboxyls; Described compd B is the compound that contains at least two aziridine rings.
Wherein, the mol ratio of carboxyl in the polymer A and the aziridine ring in the compd B is as the criterion can make polymer A and compd B generation chain extension or crosslinking reaction, and preferable is 1: 0.2-10, better is 1: 0.5-3, best is 1: 0.8-1.5.
Among the present invention, described polymer A is preferable is selected from following one or more: by a kind of homopolymer that forms in the structural unit as shown in Equation 1, and by multiple in the structural unit as shown in Equation 1 form random, alternately, block and graft copolymer, its END CAPPED GROUP is a group as shown in Equation 2.That the weight-average molecular weight of polymer A is preferable is 500-200000, and that better is 800-50000, and that best is 1000-20000.That the molecular weight distributing index of polymer A is preferable is 1-3.
Formula 1 formula 2
Wherein, n and m independently are 0 or 1; S is the integer of 0-3, s+m+n 〉=1; Preferable, when s=1, m=n=0, promptly the END CAPPED GROUP at polymer A two ends respectively has a carboxyl, totally two carboxyls; Perhaps, when m+n=1, s=0 has two carboxyls on the main chain of the polymer A that is formed by the structural unit shown in the formula 1 at least.
When the END CAPPED GROUP shown in the formula 2 when Si in the formula 1 links to each other, k is 1; When the END CAPPED GROUP shown in the formula 2 when O in the formula 1 links to each other, k is 0;
R when n is 1
1, the R when m is 1
2And R
3Independently be C
1-C
20Inferior chain alkylene, C
3-C
20Inferior cycloaliphatic alkyl, C
6-C
20Arylidene ,-NH-,-CONH-,-arbitrary combination of COO-or above-mentioned group; That preferable is C
1-C
12Inferior chain alkylene, C
3-C
12Inferior cycloaliphatic alkyl, C
6-C
12Arylidene, C
7-C
20Inferior aralkyl ,-NHR '-,-CONHR '-,-R ' CONH-,-COOR '-or-R ' COO-, wherein R ' is C
1-C
20Inferior chain alkylene; That better is C
1-C
6Inferior chain alkylene, C
3-C
6Inferior cycloaliphatic alkyl, C
6-C
10Arylidene, C
7-C
12Inferior aralkyl ,-NHR '-,-CONHR '-,-R ' CONH-,-COOR '-or-R ' COO-, wherein R ' is C
1-C
12Inferior chain alkylene.
R when n is 0
1, the R when m is 0
2And R
4Independently be hydrogen, C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
2-C
12The arbitrary combination of thiazolinyl, methanoyl or above-mentioned group; That preferable is C
1-C
12Alkyl, C
3-C
12Cycloalkyl, C
6-C
12Aryl, C
2-C
6Thiazolinyl, C
7-C
20Aralkyl, C
7-C
20Alkaryl or C
2-C
12Acyloxy.
Among the present invention, described polymer A most preferably is carboxyl propionic acid amide propyl group end-blocking polydimethylsiloxane, carboxyl propionic acid amide propyl group end-blocking PSI, carboxyl acrylamide propyl end-blocking polydimethylsiloxane, carboxyl acrylamide propyl end-blocking PSI, carboxyl benzamide propyl group end-blocking polydimethylsiloxane, or carboxyl benzamide propyl group end-blocking PSI, dimethyl siloxane-carboxyl propionic acid amide propyl-siloxane multipolymer, methylphenyl siloxane-carboxyl propionic acid amide propyl-siloxane multipolymer, dimethyl siloxane-carboxyl acrylamide propyl silicone copolymers, or methylphenyl siloxane-carboxyl acrylamide propyl silicone copolymers.
Among the present invention, commercially available the getting of described polymer A part, other can (open bright, the Yan Weilong of pier referring to patent documentation US3956353 and existing document, the preparation of carboxy-modified silicone oil, organosilicon material and application, 1999,13 (6): 7-10) disclosed method is prepared.
Among the present invention, described compd B is the compound that contains at least two aziridine rings, and it is as linking agent or chainextender.Preferable, described aziridine ring is a group as shown in Equation 3;
Formula 3
Wherein, R
5Be hydrogen, C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
2-C
12Thiazolinyl or the arbitrary combination of above-mentioned group, that preferable is C
1-C
12Alkyl, C
3-C
12Cycloalkyl, C
6-C
12Aryl, C
2-C
6Thiazolinyl, C
7-C
20Aralkyl or C
7-C
20Alkaryl.
Preferable, compd B can be aziridine lopps organic micromolecule compound as shown in Equation 4:
Formula 4
Wherein, z is 2～20 integer, preferable is 2～10 integer; R
5With aforementioned;
M is C
1-C
20Alkyl, C
4-C
20Cyclic hydrocarbon radical, perhaps their combination, perhaps C
1-C
20Alkyl and/or C
4-C
20One or more combination in cyclic hydrocarbon radical and the following groups: carbonyl, acyloxy, amide group, amino and halogen; That preferable is C
1-C
12Alkyl, C
6-C
12Cyclic hydrocarbon radical, perhaps their combination, perhaps C
1-C
12Alkyl and/or C
6-C
12One or more combination in cyclic hydrocarbon radical and the following groups: carbonyl, acyloxy, amide group, amino and halogen; M links to each other with the aziridine ring nitrogen shown in the formula 4 through suitable C atom.In the formula 4, the line between M and the N is not the single chemical bond of expression, but expression M connects 2～20 aziridine rings through suitable C atom.
Described aziridine lopps organic micromolecule compound B most preferably is:
Preferable, compd B also can be the polymkeric substance that contains the aziridine ring as shown in Equation 5;
Formula 5
Wherein, R
5With aforementioned;
R
6Be to form the homopolymerization chain, or random, alternately, the repeat unit structure of the copolymerization chain of block or graft type; That the polymerization degree of described homopolymerization chain or copolymerization chain is preferable is 10-1000; What described homopolymerization chain or copolymerization chain were preferable is polyolefin chain, organopolysiloxane chain, polyacrylic ester chain, polyurethane chain or polycarbonate chain, better for the polymerization degree be the polyolefin chain of 10-1000, the polymerization degree is the polyacrylic ester of 10-1000, the polymerization degree is the polymethacrylate of 10-1000, or the polymerization degree is the organopolysiloxane of 10-1000; Best for the polymerization degree be that the polyacrylic ester or the polymerization degree of 10-100 is the polymethacrylate of 10-100.
R
7Be nothing, C
1-C
20Inferior chain alkylene, C
3-C
20Inferior cycloaliphatic alkyl, C
6-C
20Arylidene ,-NH-,-CONH-,-arbitrary combination of COO-or above-mentioned group; That preferable is C
1-C
12Inferior chain alkylene, C
3-C
12Inferior cycloaliphatic alkyl, C
6-C
12Arylidene, C
7-C
20Inferior aralkyl ,-NHR '-,-CONHR '-,-R ' CONH-,-COOR '-or-R ' COO-, wherein R ' is C
1-C
20Inferior chain alkylene; That better is C
1-C
6Inferior chain alkylene, C
3-C
6Inferior cycloaliphatic alkyl, C
6-C
10Arylidene, C
7-C
12Inferior aralkyl ,-NHR '-,-CONHR '-,-R ' CONH-,-COOR '-or-R ' COO-, wherein R ' is C
1-C
12Inferior chain alkylene;
Work as R
7When no, z is the integer of 2-10, R
6Link to each other with the aziridine ring nitrogen through suitable C atom; Work as R
7When not being no, z is 1,2 or 3.
Among the present invention, described compd B is all commercially available to be got, also can referring to document (Girija S.Singh, Matthias D ' hooghe and Norbert De Kimpe., Chem.Rev., 2007,107,2080-2135) disclosed method is prepared.
Preferable, the composition that is used for preparing silicone elastomer of the present invention also can contain filler, to strengthen the range of application and the performance of the organic elastomer that makes behind curing reaction.The selection of filling kind and consumption can be selected according to the conventional knowledge and the prior art of concrete Application Areas.For example: precipitated silica, fumed silica, nano-calcium carbonate, diatomite, silicon powder, titanium dioxide, aluminium powder, nano zine oxide, nano aluminium oxide and Feldspar Powder etc.
Preferable, the composition that is used to prepare silicone elastomer of the present invention also can contain other chainextender except that compd B, to strengthen elastomeric range of application of prepared organic and performance.The selection of other chainextender except that compd B and consumption can be selected according to the conventional knowledge and the prior art of concrete Application Areas.For example: have two De oxazoline Huan De oxazoline compounds as shown in Equation 6, as 2,2 '-(1, the 3-phenylene) two-2-oxazoline etc.
Formula 6
The invention still further relates to a kind of silicone elastomer, it is the crosslinked or extend polymers of polymer A, its by suc as formula 7 and/or formula 8 shown in the crosslinked or chain extension of structure that forms by carboxyl in the polymer A and the aziridine ring in the compd B; Polymer A and compd B are with aforementioned.
Formula 7 formulas 8
Obviously, when described aziridine ring is as shown in Equation 3 group; Chemical bond a connects R in formula 7 or the formula 8
5, R
5With aforementioned, i.e. following structural formula:
Formula 7 formulas 8
The structure kenel of silicone elastomer of the present invention can be the tridimensional network of cross-linked polymer, also can be the end of the chain through type 7 of compd A and/or the backbone that the structure chain extension shown in the formula 8 forms.
The tensile strength of silicone elastomer of the present invention can reach 0.1-5MPa, and elongation at break can reach 100-1000%, and Young's modulus can reach 1-20MPa, and shore hardness A can reach 10-80, weightless 5% temperature T d under the nitrogen
5Be 200-400 ℃, heat decomposition temperature is 300-700 ℃.
The invention further relates to silicone elastomer of the present invention in Application for Field such as electronics, traffic and chemical industry.Particularly, it can be applicable to prepare tackiness agent or coated coating etc.; More specifically, can be applicable to prepare seal gum or composite layer paint etc., as the seal gum on the solar panel cable concentrator, environment-friendly type sizing agent, or the expediting setting type joint sealant etc.
The present invention also further relates to the method for above-mentioned silicone elastomer, and it comprises the steps: aforementioned described composition is promptly contained the composition of polymer A and compd B, mixes, and reacts, and can make silicone elastomer.
Wherein, polymer A and compd B are as previously mentioned.The mol ratio of carboxyl in the polymer A and the aziridine ring in the compd B is 1: 0.2-10, preferable is 1: 0.5-3, better is 1: 0.8-1.5.In the reaction, according to the position of the carboxyl in the compd A, and the quantity of the aziridine group in carboxyl and compd B ratio, can form the cross-linked polymer of tridimensional network, or the silicone elastomer of the backbone that forms of polymer A chain extension.
Wherein, the temperature of described reaction is preferable is-35-150 ℃, better is 0-80 ℃, best is 20-40 ℃.What the time of described reaction was preferable is 1 second-30 days, and better is 3 seconds-10 days.When the temperature of reaction was 20-30 ℃, that the time of reaction is preferable was 0.01h-168h, and that better is 0.5h-24h, and that best is 1h-5h.
Among the preparation method of the present invention, preferable also can add filler or other chainextender except that compd B in reaction system, to strengthen elastomeric range of application of prepared organic and performance.The selection of filler and other chainextender except that compd B is with aforementioned.
Among the preparation method of the present invention, reaction can be carried out in mixing tank or forcing machine.Used mixing tank can be a mixer commonly used in the Process Technology of Polymer technology, as planetary stirrer, kneader, high speed mixing roll or high-speed mixer (as the Speed Mixer of Flack Tek company) etc.
Among the present invention, but above-mentioned each optimum condition arbitrary combination promptly gets the preferred embodiments of the invention.
Except as otherwise noted, the following term that occurs in specification sheets of the present invention and claims has following implication:
Term " chain alkylene " refers to comprise to have the saturated or undersaturated chain aliphatic group of specifying carbonatoms purpose side chain or straight chain.
Term " cycloaliphatic alkyl " refers to comprise to have the saturated or undersaturated ring-shaped fat alkyl of the carbonatoms purpose of appointment.
Term " alkyl " refers to comprise to have the representative examples of saturated aliphatic alkyl of specifying carbonatoms purpose side chain or straight chain.For example, " C
1-C
10Alkyl " be meant the saturated fatty alkyl that has 1,2,3,4,5,6,7,8,9 or 10 carbon atom in the straight or branched structure, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, amyl group, hexyl, heptyl, octyl group, nonyl and decyl or the like.
Term " cycloalkyl " is meant saturated or the unsaturated monocycle of part, encircle or bridge joint carbocyclic ring substituting group more.As " C
3-C
10Cycloalkyl " have the ring of 3-10 carbon atom, as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, 1,2,3,4-tetrahydrochysene-naphthyl and two ring [2.2.2] octyl groups etc.Cycloalkyl is connected on the central element through saturated carbon atom.
Term " alkoxyl group " expression has described carbonatoms purpose ring-type or a non-annularity alkyl by what oxo bridge connected.
Term " thiazolinyl " is meant and contains straight chain, side chain or the ring-type non-aromatic hydrocarbon base that specifies number carbon atom and at least one carbon-carbon double bond.Carbon-carbon double bond of preferred existence, and can have non-fragrant carbon-carbon double bond up to four.For example, " C
2-C
6Thiazolinyl " be meant thiazolinyl with 2-6 carbon atom, as vinyl, propenyl, butenyl, 2-methyl butene base and cyclohexenyl etc.Thiazolinyl is connected on the central element through the ethylene linkage carbon atom.
Term " aryl " is meant and any stable can or encircles carbocyclic ring up to the monocycle of 7 atoms in each ring more that wherein at least one ring is an aromatic nucleus.As phenyl, naphthyl, tetralyl, 2,3-indanyl, xenyl, phenanthryl, anthryl or acenaphthenyl.In polyaromatic, and one of them ring is under the situation of non-aromatic ring, is connected on the central element through the carbon atom on the aromatic nucleus.
Term " aralkyl " is meant the group that aryl and alkyl are formed, and is connected on the central element through carbon atom on the alkyl.
Term " alkaryl " is meant the group that aryl and alkyl are formed, and is connected on the central element through carbon atom on the aryl.
Term " inferior * * yl " represents that this group links to each other with central element through two suitable atoms.
Described " arbitrary combination of group " refers to the new group that any two or more group in the described group is interconnected to form; For example, arylene links to each other with alkylidene group, forms inferior aralkyl, and it is connected with central element by an end of aryl and an end of alkyl; Again for example ,-COO-links to each other with inferior chain alkylene, formation-COOR-or-RCOO-, R is inferior chain alkylene, it is connected with central element by the-end of COO-and an end of inferior chain alkylene.
The term that the present invention relates to " elasticity " is meant that related polymer materials can produce corresponding deformation (be sheared, compress or extend) under external force, and the deformation of material can return to the characteristic near original length or shape fast after removing the external force effect.
The term that the present invention relates to " elastomerics " is meant the general name with elastomeric macromolecular compound or mixture.
Agents useful for same of the present invention and raw material except that specifying, all commercially available getting.
Positive progressive effect of the present invention is:
(1) the present invention's method of preparing silicone elastomer does not have the generation of volatile organic compounds, does not need to add heavy metal catalyst yet, meets the environmental protection demand.
(2) curing of the silicone elastomer of the present invention's preparation need not carry out under humidity environment, does not need catalyzer yet, and therefore, curing speed does not exist catalyst concn and ambient moisture influence.
(3) the present invention prepares in the method for silicone elastomer, and crosslinked or chain extending reaction is carried out on the inside of reaction system and top layer simultaneously, and speed of response is fast, and sufficient reacting is thorough, but therefore completely solidified, deeply-curing.
(4) composition that is used to prepare silicone elastomer of the present invention has good flowability, is convenient to operation processing.
(5) silicone elastomer of the present invention has the excellent comprehensive performance, as good tensile strength and elasticity, electric insulation, high-low temperature resistant, anti-ozone, weather resisteant and water tolerance etc., especially have the cohesiveness and the apparent transparency that are better than conventional silicone elastomer.Silicone elastomer of the present invention is with a wide range of applications.
Figure of description
Fig. 1 is the FTIR collection of illustrative plates of prepared polymer A in the reference example 5～8.
Fig. 2 is the apparent figure of elastomer silicone composition among the embodiment 1.
Fig. 3 is the apparent figure of prepared organic silicone elastomer among the embodiment 1.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
Among the following embodiment, part reagent and raw material sources are as follows:
The end capped polydimethylsiloxane of aminopropyl: Genesee polymers company limited.
MALEIC ANHYDRIDE, Succinic anhydried: Chemical Reagent Co., Ltd., Sinopharm Group.
TriMethylolPropane(TMP)-three [3-(2-methylaziridine base) propionic ester]: trade(brand)name F-0082, the excellent prestige in Shanghai trade Co., Ltd.
1,1 '-isophthaloyl-two (2-methylaziridine): trade(brand)name HX-752, the meticulous company limited of Yingkou, Liaoning rural area industry.
Filler white carbon black SiO
2: nano silicon, surface-area 160 ± 25m
2/ g, Evonik Degussa (China) Co., Ltd.).
Filler Al
2O
3: trade(brand)name A-Q-5,5 microns of particle diameters, Zhengzhou, Henan powder scientific ﹠ technical corporation.
The speedmixer agitator is Flack Tek company product, and it is DAC150FVZ that embodiment 1 adopts model, and all the other embodiment are DAC400FVZ.
The preparation of reference example 1 polymer A (α, the ω-end capped polydimethylsiloxane of carboxyl acrylamide propyl)
In the container that has agitator, add the end capped polydimethylsiloxane (Mw=4000 of 120g aminopropyl, 0.03mol), with 5.88g MALEIC ANHYDRIDE (0.06mol), 60 ℃ of stirring reactions 30 minutes, promptly get α, the ω-end capped polydimethylsiloxane of carboxyl acrylamide propyl, i.e. polymer A (Mw=4000, molecular weight distributing index is 1.81), structural formula is:
The preparation of reference example 2 polymer A (α, the ω-end capped polydimethylsiloxane of carboxyl propionic acid amide propyl group)
In the container that has agitator, add the end capped polydimethylsiloxane of 350g aminopropyl (Mw=1000,0.35mol) and 50g Succinic anhydried (0.5mol); 130 ℃ of stirring reactions 30 minutes, promptly get α again, the ω-end capped polydimethylsiloxane of carboxyl propionic acid amide propyl group end-blocking, i.e. polymer A (Mw=1000, molecular weight distributing index are 1.36), structural formula is:
The preparation of reference example 3 polymer A (α, the ω-Silante terminated polydimethylsiloxane of carboxyl acrylamide propyl methyl ethoxy)
In the there-necked flask that has agitator, add the hydroxy-end capped polydimethylsiloxane (Mw=32000 of 800g, come from chemical company of Japanese SHIN-ETSU HANTOTAI), heating vacuumizes and dewaters 2 hours, add amine propyl group methyldiethoxysilane (Mw=191 with syringe, Zhangjiagang Cathay China flourish new chemical materials company limited) 17.19g, 40 ℃ were reacted 3 hours down.Termination reaction when not having precipitation with the tetrabutyl titanate test, the gained reaction product is the Silante terminated polydimethylsiloxane of amine propyl group methyl ethoxy.Get the Silante terminated polydimethylsiloxane 60g of prepared aminopropyl methyl ethoxy, add MALEIC ANHYDRIDE 0.66g again, 60 ℃ of stirring reactions 30 minutes.Reaction finishes, and obtains α, the ω-Silante terminated polydimethylsiloxane of carboxyl acrylamide propyl methyl ethoxy, i.e. and polymer A (Mw=32000, molecular weight distributing index are 1.5), structural formula is:
The preparation of reference example 4 polymer A (α, the ω-end capped polydimethylsiloxane of carboxyl acrylamide propyl)
In having the there-necked flask of agitator, add the end capped polydimethylsiloxane of aminopropyl (Mw=1000,1.00mol) and 196g MALEIC ANHYDRIDE (2.00mol), 60 ℃ of stirring reactions 30 minutes.Reaction finishes, and obtains α, the ω-end capped polydimethylsiloxane of carboxyl acrylamide propyl, i.e. and polymer A (Mw=1000, molecular weight distributing index are 1.36), structural formula is:
Reference example 5～8
Dimethyl siloxane in the there-necked flask that has agitator shown in the adding table 1-aminopropyl methylsiloxane multipolymer (Jiaxing Joint Chemical Co., Ltd), and MALEIC ANHYDRIDE, 60 ℃ of stirring reactions 30 minutes, make the polymer A of reference example 5～8 respectively, molecular weight and distribution thereof are specifically as shown in table 1, and structural formula is:
The polymer A of table 1 reference example 5～8 and preparation raw material thereof
The FTIR collection of illustrative plates of polymer A is seen Fig. 1.By the FTIR collection of illustrative plates of accompanying drawing 1 as seen, the peak 1799cm of the feature of MALEIC ANHYDRIDE
-1In polymer A, disappeared, and COOH 1708cm on the collection of illustrative plates of polymer A that reaction generates
-1The place has occurred.Dimethyl siloxane-aminopropyl methylsiloxane multipolymer is at 1257cm
-1Si-(CH appears in the place
3)
2Characteristic peak, in the polymer A also at 1257cm
-1Si-(CH appears
3)
2Characteristic peak.This explanation reaction has obtained polymer A.
Embodiment 1
In the polypropylene dedicated cup of 300ml speedmixer, add polymer A and 9.34g reactant B (TriMethylolPropane(TMP)-three [3-(2-methylaziridine base) propionic ester] that 126g reference example 1 makes, 0.02mol), in the speedmixer agitator, stir 1.5min then with 3000rpm.Reactant A mixes completion of cure in the back room temperature (25 ℃) following 1 hour with reactant B, promptly get silicone elastomer (weightless 5% temperature T d under the nitrogen
5Be 324.7 ℃, heat decomposition temperature is 535.0 ℃).Before the curing reaction, the composition of being made up of polymer A and compd B has good flowability, and is workable, referring to Fig. 2.Behind the curing reaction, the prepared organic silicone elastomer is apparent transparent, referring to Fig. 3.
Embodiment 2
In the polypropylene dedicated cup of 500ml speedmixer, add polymer A and the 78g reactant B (TriMethylolPropane(TMP)-three [3-(2-methylaziridine base) propionic ester] that 400g reference example 2 makes, 0.17mol), in the speedmixer agitator, stir 1.5min then with 3000rpm.Reactant A mixes 0.5h completion of cure under the room temperature of back with reactant B, promptly get silicone elastomer.
Embodiment 3
In the polypropylene dedicated cup of 100ml speedmixer, add the polymer A and the 0.58g reactant B (TriMethylolPropane(TMP)-three [3-(2-methylaziridine base) propionic ester]) of 60g reference example 3, in the speedmixer agitator, stir 1.5min then with 3000rpm.Polymer A is mixed 24h completion of cure under the room temperature of back with compd B, promptly get silicone elastomer.
Embodiment 4～6 introduces chainextender and is cured
In the polypropylene dedicated cup of 100ml speedmixer, add polymer A and the following two kinds of compd Bs that reference example 4 makes by table 2 prescription: linking agent (TriMethylolPropane(TMP)-three [3-(2-methylaziridine base) propionic ester]) and chainextender (1,1 '-isophthaloyl-two (2-methylaziridine)).In the speedmixer agitator, stir 1.5min then, be cured, promptly make the silicone elastomer of embodiment 4～6 respectively by the set time shown in the table 2 with 3000rpm.
Embodiment 7～12 regulates curing speed by different polymer A and compd B
Respectively with reference example 5～7 prepared polymer A and compd B (1,1 '-isophthaloyl-two (2-methylaziridine) or TriMethylolPropane(TMP)-three [3-(2-methylaziridine base) propionic ester]) press in the polypropylene dedicated cup of table 2 consumption adding speedmixer, speed with 3000rpm is mixed 2min in the speedmixer agitator then, be cured by the set time shown in the table 2, promptly make the silicone elastomer of embodiment 7～12 respectively.
Embodiment 13
Polymer A and compd B (TriMethylolPropane(TMP)-three [3-(2-methylaziridine base) propionic ester]) and filler Al with gained
2O
3(200～300 orders, come from Chemical Reagent Co., Ltd., Sinopharm Group) be placed in the polypropylene dedicated cup of speedmixer, speed with 3000rpm is mixed 2min in the speedmixer agitator then, is cured by the set time shown in the table 2, promptly gets silicone elastomer.
Embodiment 14～15
Polymer A and compd B (1,1 '-isophthaloyl-two (2-methylaziridine) or TriMethylolPropane(TMP)-three [3-(2-methylaziridine base) propionic ester]) and filler Al that reference example 6 is made
2O
3Put into the polypropylene dedicated cup of speedmixer, the speed with 3000rpm is mixed 1.5min in the speedmixer agitator then, is cured by the set time shown in the table 2, promptly makes the silicone elastomer of embodiment 14～15 respectively.
Embodiment 16～18
With reference example 5 prepared polymer A and compd B (TriMethylolPropane(TMP)-three [3-(2-methylaziridine base) propionic ester]), and filler white carbon black SiO
2Put into the polypropylene dedicated cup of speedmixer, the speed with 3000rpm is mixed 2min in the speedmixer agitator then, is cured by the set time shown in the table 2, promptly makes the silicone elastomer of embodiment 16～18 respectively.
Embodiment 19～21
With reference example 8 polymer A and compd B (TriMethylolPropane(TMP)-three [3-(2-methylaziridine base) propionic ester]), and filler white carbon black SiO
2And/or Al
2O
3Put in the polypropylene dedicated cup of speedmixer, the speed with 3000rpm is mixed 1min in the speedmixer agitator then, is cured by the set time shown in the table 2, promptly makes the silicone elastomer of embodiment 19～21 respectively.
Embodiment 22～24
With reference example 5 and 8 prepared polymer A and compd B (TriMethylolPropane(TMP)-three [3-(2-methylaziridine base) propionic ester]), and filler white carbon black SiO
2And/or aluminium oxide Al
2O
3Put in the polypropylene dedicated cup of speedmixer, the speed with 3000rpm is mixed 2min in the speedmixer agitator then, is cured by the set time shown in the table 2, promptly makes the silicone elastomer of embodiment 22～24 respectively.
The organosilicone elastic preparation actual conditions of table 2 embodiment 1～24
The performance of the silicone elastomer of effect EXAMPLE Example 4～6,13～24
With embodiment 4～6,13～24 silicone elastomers that make carry out following performance test, and test result sees Table 3.Each test is all carried out for 50% time at normal pressure and temperature and relative humidity, except as otherwise noted.Concrete testing method is as follows:
1, thermogravimetric analysis
Embodiment 13～24 is by the test of Pyris-1TGA thermogravimetric analyzer, and test condition is the temperature rise rate of 10/min, tests in air atmosphere.
2, Mechanics Performance Testing: adopt Instron material-testing machine (Instron Corporation, model 5569), test according to USS ASTM-D412 method.
3, GPC test: adopt PE200 Serlies GPC (RI detector) instrument, test according to USS ASTM D5296-05.
4, electrical performance testing
(1) thermal conductivity test: LFA447 nonoflash tester (Netzsch company)
(2) volume specific resistance: Agilent 4339B high resistant instrument.
(3) specific inductivity: Agilent E4980A Precision LCR Meter instrument test, test frequency 1MHz.
(4) dielectric strength: macromolecular material research centre, Shanghai is according to standard A STM 3755 tests.
Table 3 embodiment 4～6,13～24 performance test data
Claims (29)
1. composition that is used to prepare silicone elastomer, it is characterized in that it contains: polymer A and compd B, described polymer A are the silicone oil polymkeric substance that contains at least two carboxyls; Described compd B is the compound that contains at least two aziridine rings.
2. composition as claimed in claim 1 is characterized in that: the mol ratio of carboxyl in the described polymer A and the aziridine ring in the compd B is 1: 0.2-10.
3. composition as claimed in claim 2 is characterized in that: the mol ratio of carboxyl in the described polymer A and the aziridine ring in the compd B is 1: 0.5-3.
4. composition as claimed in claim 3 is characterized in that: the mol ratio of carboxyl in the described polymer A and the aziridine ring in the compd B is 1: 0.8-1.5.
5. as each described composition of claim 1～4, it is characterized in that: described polymer A is selected from one or more in following: by a kind of homopolymer that forms in the structural unit as shown in Equation 1, and by multiple in the structural unit as shown in Equation 1 form random, alternately, block and graft copolymer, its END CAPPED GROUP is a group as shown in Equation 2;
Formula 1 formula 2
Wherein, n and m independently are 0 or 1; S is the integer of 0-3, s+m+n 〉=1;
When the END CAPPED GROUP shown in the formula 2 when Si in the formula 1 links to each other, k is 1; When the END CAPPED GROUP shown in the formula 2 when O in the formula 1 links to each other, k is 0;
R when n is 1
1, the R when m is 1
2And R
3Independently be C
1-C
20Inferior chain alkylene, C
3-C
20Inferior cycloaliphatic alkyl, C
6-C
20Arylidene ,-NH-,-CONH-,-arbitrary combination of COO-or above-mentioned group;
R when n is 0
1, the R when m is 0
2And R
4Independently be hydrogen, C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
2-C
12The arbitrary combination of thiazolinyl, methanoyl or above-mentioned group.
6. composition as claimed in claim 5 is characterized in that: s=1, and m=n=0, perhaps m+n=1, s=0 has two carboxyls on the main chain of the polymer A that is formed by the structural unit shown in the formula 1 at least.
7. as claim 5 or 6 described compositions, it is characterized in that:
Described R when n is 1
1, the R when m is 1
2And R
3Independently be C
1-C
12Inferior chain alkylene, C
3-C
12Inferior cycloaliphatic alkyl, C
6-C
12Arylidene, C
7-C
20Inferior aralkyl ,-NHR '-,-CONHR '-,-R ' CONH-,-COOR '-or-R ' COO-, wherein R ' is C
1-C
20Inferior chain alkylene;
Described R when n is 0
1, the R when m is 0
2And R
4Independently be C
1-C
12Alkyl, C
3-C
12Cycloalkyl, C
6-C
12Aryl, C
2-C
6Thiazolinyl, C
7-C
20Aralkyl, C
7-C
20Alkaryl or C
2-C
12Acyloxy.
8. composition as claimed in claim 7 is characterized in that:
Described R when n is 1
1, the R when m is 1
2And R
3Independently be C
1-C
6Inferior chain alkylene, C
3-C
6Inferior cycloaliphatic alkyl, C
6-C
10Arylidene, C
7-C
12Inferior aralkyl ,-NHR '-,-CONHR '-,-R ' CONH-,-COOR '-or-R ' COO-, wherein R ' is C
1-C
12Inferior chain alkylene.
9. as each described composition of claim 1～4, it is characterized in that: described polymer A is a carboxyl propionic acid amide propyl group end-blocking polydimethylsiloxane, carboxyl propionic acid amide propyl group end-blocking PSI, carboxyl acrylamide propyl end-blocking polydimethylsiloxane, carboxyl acrylamide propyl end-blocking PSI, carboxyl benzamide propyl group end-blocking polydimethylsiloxane, or carboxyl benzamide propyl group end-blocking PSI, dimethyl siloxane-carboxyl propionic acid amide propyl-siloxane multipolymer, methylphenyl siloxane-carboxyl propionic acid amide propyl-siloxane multipolymer, dimethyl siloxane-carboxyl acrylamide propyl silicone copolymers, or methylphenyl siloxane-carboxyl acrylamide propyl silicone copolymers.
10. as each described composition of claim 1～9, it is characterized in that: the weight-average molecular weight of described polymer A is 500-200000.
11. composition as claimed in claim 10 is characterized in that: the weight-average molecular weight of described polymer A is 800-50000.
12. composition as claimed in claim 11 is characterized in that: the weight-average molecular weight of described polymer A is 1000-20000.
13. as each described composition of claim 1～12, it is characterized in that: the molecular weight distributing index of described polymer A is 1-3.
14. as each described composition of claim 1～13, it is characterized in that: described aziridine ring is a group as shown in Equation 3;
Formula 3
Wherein, R
5Be hydrogen, C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
2-C
12Thiazolinyl or the arbitrary combination of above-mentioned group.
15. composition as claimed in claim 14 is characterized in that: described R
5Be C
1-C
12Alkyl, C
3-C
12Cycloalkyl, C
6-C
12Aryl, C
2-C
6Thiazolinyl, C
7-C
20Aralkyl or C
7-C
20Alkaryl.
16. as each described composition of claim 1～15, it is characterized in that: described compd B is one or more in following:
(1) aziridine lopps organic micromolecule compound as shown in Equation 4:
Formula 4
Wherein, z is 2～20 integer; R
5Described with claim 12 or 13;
M is C
1-C
20Alkyl, C
4-C
20Cyclic hydrocarbon radical, perhaps their combination, perhaps C
1-C
20Alkyl and/or C
4-C
20One or more combination in cyclic hydrocarbon radical and the following groups: carbonyl, acyloxy, amide group, amino and halogen; The C atom that the M warp suits links to each other with the aziridine ring nitrogen in the formula 4; And
(2) polymkeric substance of repeating unit as shown in Equation 5;
Formula 5
Wherein, R
5Described with claim 13 or 14;
R
6Be to form the homopolymerization chain, or random, alternately, the repeat unit structure of the copolymerization chain of block or graft type; The polymerization degree of described homopolymerization chain or copolymerization chain is 10-1000;
R
7Be nothing, C
1-C
20Inferior chain alkylene, C
3-C
20Inferior cycloaliphatic alkyl, C
6-C
20Arylidene ,-NH-,-CONH-,-arbitrary combination of COO-or above-mentioned group;
Work as R
7When no, z is the integer of 2-10, R
6Link to each other with the aziridine ring nitrogen through suitable C atom; Work as R
7When not being no, z is 1,2 or 3.
17. composition as claimed in claim 16 is characterized in that:
Described M is C
1-C
12Alkyl, C
6-C
12Cyclic hydrocarbon radical, perhaps their combination, perhaps C
1-C
12Alkyl and/or C
6-C
12One or more combination in cyclic hydrocarbon radical and the following groups: carbonyl, acyloxy, amide group, amino and halogen;
Described homopolymerization chain or copolymerization chain are that the polymerization degree is the polyolefine of 10-1000, and the polymerization degree is the polyacrylic ester of 10-1000, and the polymerization degree is the polymethacrylate of 10-1000, or the polymerization degree is the organopolysiloxane of 10-1000;
Described R
7Be C
1-C
12Inferior chain alkylene, C
3-C
12Inferior cycloaliphatic alkyl, C
6-C
12Arylidene, C
7-C
20Inferior aralkyl ,-NHR '-,-CONHR '-,-R ' CONH-,-COOR '-or-R ' COO-, wherein R ' is C
1-C
20Inferior chain alkylene.
18. composition as claimed in claim 17 is characterized in that:
Described homopolymerization chain is that the polymerization degree is that the polyacrylic ester or the polymerization degree of 10-100 is the polymethacrylate of 10-100;
Described R
7Be C
1-C
6Inferior chain alkylene, C
3-C
6Inferior cycloaliphatic alkyl, C
6-C
10Arylidene, C
7-C
12Inferior aralkyl ,-NHR '-,-CONHR '-,-R ' CONH-,-COOR '-or-R ' COO-, wherein R ' is C
1-C
12Inferior chain alkylene.
19. as each described composition of claim 1～13, it is characterized in that: described compd B is selected from one or more in following:
20., it is characterized in that as each described composition of claim 1～19: the described composition that is used for preparing silicone elastomer, also contain filler and/or other chainextender except that compd B.
21. composition as claimed in claim 20 is characterized in that: described filler is selected from one or more in precipitated silica, fumed silica, nano-calcium carbonate, diatomite, silicon powder, titanium dioxide, aluminium powder, nano zine oxide, nano aluminium oxide and the Feldspar Powder;
Described other chainextender except that compd B is to have two De oxazoline Huan De oxazoline compounds as shown in Equation 6;
Formula 6.
22. a silicone elastomer is characterized in that: it is the crosslinked or extend polymers of polymer A, its by suc as formula 7 and/or formula 8 shown in by carboxyl in the polymer A and the crosslinked or chain extension of the formed structure of aziridine ring in the compd B; Polymer A is with each is described in claim 1 and 5～13; Compd B is with each is described in claim 1 and 14～19, when compd B with 14～19 each when described, chemical bond a connects R in formula 7 or the formula 8
5, R
5Described with claim 14 or 15;
Formula 7 formulas 8.
23. the application of silicone elastomer as claimed in claim 22 in preparation tackiness agent or coated coating.
24. application as claimed in claim 23 is characterized in that: described tackiness agent is a seal gum; Described coated coating is a composite layer paint.
25. the preparation method of silicone elastomer as claimed in claim 22 is characterized in that it comprises the steps: to mix as each described composition of claim 1～21, reacts, and can make silicone elastomer.
26. method as claimed in claim 25 is characterized in that: the temperature of described reaction is 0-80 ℃.
27. method as claimed in claim 25 is characterized in that: the time of described reaction is 1 second-30 days.
28. method as claimed in claim 25 is characterized in that: described temperature is 20-30 ℃, and the time of described reaction is 0.01h-168h.
29. method as claimed in claim 28 is characterized in that: the time of described reaction is 1h-5h.
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