Background technology
Coupling agent is a kind of functional compounds that can strengthen bond properties between inorganic substance and organic substance.In coupling agent molecule, contain two kinds of groups of different nature, a kind of is the group of close inorganics, hydroxyl normally, can with inorganic material surface react with; Another is close organic organic group, can with organic polymer generation physical action or chemical reaction.Therefore coupling agent is often used to improve the interface interaction between inorganics and organism, improves the bond properties at organic constituent and inorganic materials interface.
Silane coupling agent is a most important class in coupling agent, in fields such as matrix material, rubber, tackiness agent and coating, is widely used.Silane coupling agent can improve mineral filler and interlaminar resin consistency, improves composite material combination property.Silane coupling agent can also increase the cohesive strength of binding agent, sealing agent and coating, the water-fast performance such as weather-proof.In tackiness agent, add silane coupling agent can not only improve bond strength, and can also improve weather resistance and the wet and heat ageing resistant performance of tackiness agent.For example, although polyurethane adhesive has higher bounding force to many materials, its weather resistance is not ideal, adds silane coupling agent can improve its weather resistance.In addition, for polyurethane tackifier, under hot and humid condition, easily wreck, add silane coupling agent also can significantly improve its wet-hot aging performance.Silane coupling agent, for coating, can reduce the corrosion of wet environment floating coat and peeling off of paint film, improves scuff resistance and environment resistant.Silane coupling agent is used in coating also can play pigment dispersing agent, and they can be firmly bonded on various mineral dyes and filler, reduces the viscosity of coating, improves the dispersiveness of filler, thereby improves opacifying power, improves weather resistance and the scrubbability of coating.
Polyarylester, polyaramide, PAEK, polyarylsulphone, polycarbonate, resol, Polybenzoxazine, polybenzimidazole and polyphenylene oxide etc. are the important macromolecule resin materials containing aromatic nucleus of a class, in its macromolecular chain, contain strong polar group and aromatic group, this resinoid mechanical property and heat resistance are outstanding, itself can directly be used as engineering plastics, the high performance composite that can make together with filler, therefore, in industry manufacture, field of aerospace technology, there is important application prospect.Filler is widely used in resin, rubber and coating, in order to improve mechanical property and the processing characteristics of body material, and reduces costs.Filler can be powdery, cotton-shaped or fibrous material, as calcium carbonate, carbon black, white carbon black and glass fibre etc., for matrix resin, can prepare all kinds of matrix materials with superperformance.But because filling surface multi-band has hydrophilic radical, with organic resin, the consistency particularly containing between aromatic group resin is poor, affects the performance of matrix material.The goods made from it are in water surrounding or under high humidity, faint bounding force between filler and matrix resin can lose efficacy, therefore, filler is used coupling agent to carry out surface treatment conventionally, coupled dose of institute of inorganic filler surface covered, the organic group of coupling agent makes mineral filler have hydrophobic and the performance of close resin, thereby has greatly improved the consistency of filler and organic matrix, makes the matrix material of excellent performance.
Traditional silane coupling agent, as KH550, KH560 and KH570 etc., with a tri-alkoxy (methoxy or ethoxy) silane group, can be called single armed silane coupling agent.Three cross-linking set of the in use maximum generation of silica-based part of this silane coupling agent, relatively little with the clinging power of filling surface, not strong with the macromolecule resin avidity containing aromatic nucleus, limited to a certain extent the raising of the various performances of matrix material.For remedy such and insufficient, can use tackifier to increase bonding effect, but tackifier just play physically adhesive effect, limited to the bond strength contribution of reinforcing filler and interlaminar resin.
Having a kind of pair-Trimethoxy silane coupling agent of reported in literature, can produce six cross-linking set, is the twice of traditional single armed trialkoxy silane, can improve coupling agent at the bounding force (P.A.Toensmeier of interface region, Modern Plastics (1987), Vol.5,55).
CN102329336A discloses single armed and many ureido silanes of both arms coupling agent, and the adhesive aid using it as room temp solidified organo-silicone rubber (RTV) composition, can obtain room temp solidified (RTV) organopolysiloxane composition of bond properties, excellent storage stability.
US6261638 discloses a kind of " multi-functional base silane ", for preventing the composition of metallic corrosion, this " multi-functional base silane " contains two or three water-disintegrable silane groups, this patent documentation is that example illustrates that this one type of silane can improve the erosion resistance of metal in sodium chloride solution greatly with the two silica-based ethane of triethoxy of 1,2-.
But it is not the disclosed coupling agent cross-linking set of above-mentioned document is few, with matrix resin, particularly, strong with the bonding force containing aromatic group resin.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of aryl multi-arm silane, in this aryl multi-arm silane molecule, contain aryl, urea groups, amido and a plurality of water-disintegrable silane group, the functional group in silane molecule can regulate and control.When this aryl multi-arm silane is used as coupling agent treatment inorganic filler surface, except having the advantage of common silane coupling agent, can further strengthen matrix resin that mineral filler and polarity are strong and containing the bounding force of aromatic group macromolecule resin, improve the over-all properties of matrix material.
Technical scheme of the present invention is as follows:
An aryl multi-arm silane coupling agent, have formula (I), (II) or (III) shown in structure:
In formula (I), (II), (III), R
1represent the alkylidene group, alkenylene, arylidene of straight chain shape, a chain or ring-type that carbonatoms is 1~15 or the group that they combine;
R
2represent alkyl, thiazolinyl, aryl, haloalkyl, halogenated aryl that carbonatoms is 1~18, or, the organic group of epoxy group(ing), third rare acyl group, methacryloyl, sulfydryl, amino or cyano group there is;
R
3represent alkoxyl group, acyloxy or halogen atom;
N is 0,1 or 2.
According to the present invention, preferred, in formula (I), (II), (III), R
1represent the alkylidene group, alkenylene, arylidene of straight chain shape, a chain or ring-type that carbonatoms is 1~12 or the group that they combine;
Further preferred, R
1represent methylene radical, ethylidene, propylidene, isopropylidene, butylidene, octylene, tetramethylene, hexa-methylene, eight methylene radical, decamethylene, ring propylidene, ring butylidene, cyclohexylene, vinylidene, propenylidene, crotonylidene or phenylene, and the group being formed by above-mentioned alkylidene group and arylidene bonding;
In the group being formed by alkylidene group and arylidene bonding, alkylidene group is preferably methylene radical, ethylidene, propylidene or cyclohexylidene, and arylidene is preferably phenylene.
According to the present invention, preferred, in formula (I), (II), (III), R
2represent alkyl, thiazolinyl, aryl, haloalkyl, halogenated aryl that carbonatoms is 1~14, or, the organic group of epoxy group(ing), third rare acyl group, methacryloyl, sulfydryl, amino or cyano group there is, further preferred, R
2represent methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, cyclopropyl, cyclobutyl, vinyl, allyl group, alkene butyl, phenyl, o-methyl-phenyl-, between aminomethyl phenyl, p-methylphenyl, adjacent xenyl, between xenyl, to xenyl, Alpha-Naphthyl, betanaphthyl, 1-anthryl, 2-anthryl, 1-phenanthryl, 2-phenanthryl, chloromethyl, chloroethyl, chloropropyl, chloro-phenyl-, Chloro-O-Phenyl, between chloro-phenyl-, rubigan, glycidoxy methyl, glycidoxy ethyl, third rare acyl methyl, acryloyl ethyl, methacryloyl methyl, methacryloyl ethyl, ethyl sulfydryl, butyl sulfydryl, amino-ethyl, aminopropyl, cyano ethyl or cyanopropyl,
More preferably methyl, ethyl, phenyl, be particularly preferably methyl.
According to the present invention, preferred, in formula (I), (II), (III), R
3represent methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, methyl ketonic oxygen base, ethyl ketonic oxygen base, n-propyl ketonic oxygen base, sec.-propyl ketonic oxygen base, normal-butyl ketonic oxygen base, isobutyl-ketonic oxygen base, sec-butyl ketonic oxygen base, tertiary butyl ketonic oxygen base, fluorine atom, chlorine atom, bromine atoms, iodine atom.
According to the present invention, preferred, in formula (I), (II), (III), n preferably 0 or 1, and particularly preferably 0.
The present invention also provides a kind of preparation method of aryl multi-arm silane coupling agent, utilizes the method also can prepare silane coupling agent composition, contains aryl multi-arm silane and isocyanato silanes component in said composition, and component and the performance of composition are adjustable.
A preparation method for aryl multi-arm silane coupling agent, step is as follows:
(1) aromatic polycarboxylic amine is dissolved in organic solvent, or isocynate silane is dissolved in organic solvent, mix, obtain aromatic polycarboxylic amine aqueous solution or isocynate silane solution;
Described aromatic polycarboxylic amine is 1,3,5-triaminobenzene or 3,3 ', 4, and 4 '-biphenyl tetramine, described aromatic polycarboxylic amine or isocynate silane are 0.3~2mol/L with the molecular volume ratio of organic solvent;
Described organic solvent is chloroform, methylene dichloride, tetrahydrofuran (THF), ether, bis-Evil ring, dimethyl formamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, acetonitrile, acetone, benzene, toluene or pyridine;
(2) isocynate silane is dropwise joined in the aromatic polycarboxylic amine aqueous solution that step (1) obtains, or aromatic polycarboxylic amine is dropwise joined in the isocynate silane solution that step (1) obtains;
Control temperature of reaction at 10~60 ℃, under stirring logical condition of nitrogen gas, react 1~8h, remove solvent, obtain.
According to the present invention, preferred, the organic solvent described in step (1) is methylene dichloride or tetrahydrofuran (THF).
According to the present invention, preferably, described isocynate silane is isocyanic ester propyl trimethoxy silicane, isocyanic ester propyl-triethoxysilicane, isocyanic ester sec.-propyl Trimethoxy silane, isocyanic ester sec.-propyl triethoxyl silane, isocyanic ester isopropylidene Trimethoxy silane, isocyanic ester isopropylidene triethoxyl silane, isocyanic ester propyl chloride methyl dimethoxysilane or isocyanic ester propyl chloride methyldiethoxysilane.
According to the present invention, preferred, in step (2), control temperature of reaction and be that to control temperature of reaction after 10~20 ℃ of reaction 1~2h be 30~40 ℃ of reaction 2-3h again.
According to the present invention, preferred, the method for removing solvent in step (2) is underpressure distillation.
According to the present invention, preferably, when aromatic polycarboxylic amine is 1,3,5-triaminobenzene, and while isocynate silane dropwise being joined in aromatic polycarboxylic amine aqueous solution in step (2), control isocynate silane and 1,3,5-triaminobenzene mol ratio is 3:1, must contain the aryl three arm silane coupling agents of many urea groups;
Control isocynate silane and 1,3,5-triaminobenzene mol ratio (2~1): 1, the coupling agent composition of the aryl both arms silane that must contain the aryl single armed silane of urea groups, amino and contain urea groups, amino;
Control isocynate silane and 1,3,5-triaminobenzene mol ratio (3~2): 1, must contain the aryl both arms silane of urea groups, amino and contain urea groups and the coupling agent composition of three arm silane of aryl.
According to the present invention, preferably, when aromatic polycarboxylic amine is 1,3,5-triaminobenzene, and while aromatic polycarboxylic amine dropwise being joined in isocynate silane solution in step (2), control 1, the mol ratio of 3,5-triaminobenzene and isocynate silane is 1:(3~4), obtain the coupling agent composition containing isocynate silane and aryl three arm silane.
According to the present invention, preferably, when aromatic polycarboxylic amine is 3,3 ', 4,4 '-biphenyl tetramine, and while isocynate silane dropwise being joined in aromatic polycarboxylic amine aqueous solution in step (2), control isocynate silane and 3,3 ', 4,4 '-biphenyl tetramine mol ratio is 3:1, obtains the aryl three arm silane coupling agents that simultaneously contain urea groups, amino;
Control isocynate silane and 3,3 ', 4,4 '-biphenyl tetramine mol ratio is 4:1, must contain the aryl four arm silane coupling agents of urea groups;
Control isocynate silane and 3,3 ', 4,4 '-biphenyl tetramine mol ratio (3~4): 1, the coupling agent composition of the aryl four arm silane that must contain the aryl three arm silane of urea groups, amino and contain urea groups;
Control isocynate silane and 3,3 ', 4,4 '-biphenyl tetramine mol ratio (2~3): 1, the coupling agent composition of the aryl three arm silane that must contain the aryl two arm silane of urea groups, amino and contain urea groups, amino;
Control isocynate silane and 3,3 ', 4,4 '-biphenyl tetramine mol ratio (1~2): 1, the coupling agent composition of the aryl two arm silane that must contain the aryl single armed silane coupling agent of urea groups, amino and contain urea groups, amino.
According to the present invention, preferably, when aromatic polycarboxylic amine is 3,3 ', 4,4 '-biphenyl tetramine, and while aromatic polycarboxylic amine dropwise being joined in isocynate silane solution in step (2), control isocynate silane and 3,3 ', 4, the mol ratio of 4 '-biphenyl tetramine is (5~4): 1 obtains the composition of aryl four arm silane coupling agents and isocynate silane.
According to the present invention, preferred, the reactant described in step (1) and solvent all carry out Non-aqueous processing in advance.
Principle of the present invention is:
By aromatic polycarboxylic amine and isocyanato silanes, single step reaction in organic solvent completes, by controlling order of addition(of ingredients) and the mol ratio of polyamine and isocynate silane, the synthetic aryl multi-arm silane coupling agent containing different functional groups and different functionality, and the composition that contains aryl multi-arm silane coupling agent and isocyanato silanes coupling agent.In preparation method, by the change of forward and backward phase temperature of reaction, adjust polymerization rate, the raising of late phase reaction temperature can be accelerated the speed of response because reactant reduces and reaction steric hindrance reduces.
In the present invention, the reaction formula of 1,3,5-triaminobenzene and isocyanato silanes different mol ratio is as follows:
In the present invention, 3,3 ', 4, the reaction formula of 4 '-biphenyl tetramine and isocyanato silanes different mol ratio is as follows:
Isocynate silane of the present invention, its structure is suc as formula shown in (IV):
In formula (IV), R
1, R
2, R
3implication with the implication of n and formula (I), (II) and (III) is identical.
The invention has the advantages that:
1, aryl multi-arm silane provided by the invention is compared with traditional silane coupling agent as coupling agent, when processing material interface, can provide more cross-linking set, makes the bounding force of material and matrix resin stronger.
2, aryl multi-arm silane coupling agent provided by the invention contains polarity ureido groups, this group can with matrix resin in polar group produce stronger physical action and chemical action, as coupling agent, can improve the bonding force of filler component and matrix resin.
3. aryl multi-arm silane provided by the invention contains aromatic yl group, has consistency better with Fu Fangji class engineering resin material, as coupling agent, can effectively strengthen the affinity with such matrix resin.
4, preparation method of the present invention is easy and simple to handle, and reaction time is short, and productive rate is high, and in reaction process without using catalyzer, product is pure, aftertreatment is simple.
Embodiment
Below by specific embodiment, the present invention will be further described, but be not limited to this.
It should be noted that, in the following embodiments, Me represents methyl, and Et represents ethyl.
In embodiment, raw material used is conventional reagent, and equipment used is conventional equipment, commercial product.
Embodiment 1
By 1 of 0.1mol (12.32g), 3,5-triaminobenzene and 200ml methylene dichloride add in the four-hole round-bottomed flask that dropping funnel, agitator and thermometer are housed, and logical nitrogen, stirs, and dropwise add 0.3mol (61.58g) isocyanic ester propyl trimethoxy silicane, keep 10 ℃ of reaction 2h of temperature of reaction, temperature increase to 35 ℃ continues reaction 2h afterwards, and methylene dichloride is removed in distillation, obtain that target compound-(I-1), yield is 98.7%.
For target compound-(I-1), by
1h-NMR and
13c-NMR analysis confirmation.
1h-NMR (CDCl
3, ppm): δ 7.87 (s, C
6h
3); δ 6.0 (s, NH), δ 3.38 (t, CH
2cH
2cH
2si (OCH
3)
3), δ 1.6 (m, CH
2cH
2cH
2si (OCH
3)
3), δ 0.58 (t, CH
2cH
2cH
2si (OCH
3)
3), δ 3.55 (s, CH
2cH
2cH
2si (OCH
3)
3);
13c-NMR (CDCl
3, ppm): δ 108.9 (C
6h
3), δ 136.3 (C
6h
3(replacement)), δ 154.3 (C=O), δ 45.6 (CH
2cH
2cH
2si (OCH
3)
3), δ 24.8 (CH
2cH
2cH
2si (OCH
3)
3), δ 12.5 (CH
2cH
2cH
2si (OCH
3)
3), δ 50.2 (CH
2cH
2cH
2si (OCH
3)
3).
Embodiment 2
By 3 of 0.1mol (21.43g), 3 ', 4,4 '-biphenyl tetramine and 200ml methylene dichloride add in the four-hole round-bottomed flask that dropping funnel, agitator and thermometer are housed, logical nitrogen, stir, dropwise add 0.3mol (61.58g) isocyanic ester propyl trimethoxy silicane, keep 10 ℃ of reaction 2h of temperature of reaction, temperature increase to 40 ℃ continues reaction 3h afterwards, methylene chloride is removed in distillation, obtains that target compound-(II-1), yield is 95.6%.
For target compound-(II-1), by
1h-NMR and
13c-NMR analysis confirmation.
1H-NMR(CDCl
3,ppm):δ6.87-8.05(m,C
12H
6),δ6.08(s,NH),δ6.27(s,NH
2),δ3.42(t,CH
2CH
2CH
2Si(OCH
3)
3),δ1.58(m,CH
2CH
2CH
2Si(OCH
3)
3),δ0.61(t,CH
2CH
2CH
2Si(OCH
3)
3),δ3.58(s,CH
2CH
2CH
2Si(OCH
3)
3);
13C-NMR(CDCl
3,ppm):δ114.8-142.3(C
12H
6),δ155.6(C=O),δ46.8(CH
2CH
2CH
2Si(OCH
3)
3),δ25.9(CH
2CH
2CH
2Si(OCH
3)
3),δ11.4(CH
2CH
2CH
2Si(OCH
3)
3),δ49.3(CH
2CH
2CH
2Si(OCH
3)
3)。
Embodiment 3
By 3 of 0.1mol (21.43g), 3 ', 4,4 '-biphenyl tetramine and 300ml methylene dichloride add in the four-hole round-bottomed flask that dropping funnel, agitator and thermometer are housed, logical nitrogen, stir, dropwise add 0.4mol (82.11g) isocyanic ester propyl trimethoxy silicane, keep 10 ℃ of reaction 2h of temperature of reaction, temperature increase to 45 ℃ continues reaction 3h afterwards, methylene chloride is removed in distillation, obtains that target compound-(III-1), yield is 96.7%.
For target compound-(III-1), by
1h-NMR and
13c-NMR analysis confirmation.
1H-NMR(CDCl
3,ppm):δ7.51-8.05(m,C
12H
6),δ6.05(s,NH),δ3.43(t,CH
2CH
2CH
2Si(OCH
3)
3),δ1.63(m,CH
2CH
2CH
2Si(OCH
3)
3),δ0.55(t,CH
2CH
2CH
2Si(OCH
3)
3),δ3.59(s,CH
2CH
2CH
2Si(OCH
3)
3);
13C-NMR(CDCl
3,ppm):δ116.5-135.2(C
12H
6),δ153.2(C=O),δ46.2(CH
2CH
2CH
2Si(OCH
3)
3),δ24.1(CH
2CH
2CH
2Si(OCH
3)
3),δ13.2(CH
2CH
2CH
2Si(OCH
3)
3),δ50.6(CH
2CH
2CH
2Si(OCH
3)
3)。
Embodiment 4
By 3 of 0.1mol (21.43g), 3 ', 4,4 '-biphenyl tetramine and 300ml methylene dichloride add in the four-hole round-bottomed flask that dropping funnel, agitator and thermometer are housed, logical nitrogen, stir, dropwise add 0.35mol (71.85g) isocyanic ester propyl trimethoxy silicane, keep 10 ℃ of reaction 2h of temperature of reaction, temperature increase to 40 ℃ continues reaction 3h afterwards, methylene chloride is removed in distillation, obtains the composition of the aryl three arm silane that contain urea groups, amino and the aryl four arm silane that contain urea groups.
Embodiment 5~9
With isocyanic ester propyl-triethoxysilicane, isocyanic ester isopropylidene Trimethoxy silane, isocyanic ester isopropylidene triethoxyl silane, isocyanic ester propyl chloride methyl dimethoxysilane, isocyanic ester propyl chloride methyldiethoxysilane, replace isocyanic ester Trimethoxy silane respectively, all the other conditions are with embodiment 1, obtain target compound (I-2)-(I-6)
Embodiment 9~13
With isocyanic ester propyl-triethoxysilicane, isocyanic ester isopropylidene Trimethoxy silane, isocyanic ester isopropylidene triethoxyl silane, isocyanic ester propyl chloride methyl dimethoxysilane, isocyanic ester propyl chloride methyldiethoxysilane, replace isocyanic ester Trimethoxy silane respectively, all the other conditions are with embodiment 2, obtain target compound (II-2)-(II-6)
Embodiment 14~18
With isocyanic ester propyl-triethoxysilicane, isocyanic ester isopropylidene Trimethoxy silane, isocyanic ester isopropylidene triethoxyl silane, isocyanic ester propyl chloride methyl dimethoxysilane, isocyanic ester propyl chloride methyldiethoxysilane, replace isocyanic ester Trimethoxy silane respectively, all the other conditions are with embodiment 3, obtain target compound (III-2)-(III-6)
Embodiment 19~23
With isocyanic ester propyl-triethoxysilicane, isocyanic ester isopropylidene Trimethoxy silane, isocyanic ester isopropylidene triethoxyl silane, isocyanic ester propyl chloride methyl dimethoxysilane, isocyanic ester propyl chloride methyldiethoxysilane, replace isocyanic ester Trimethoxy silane respectively, all the other conditions, with embodiment 4, obtain the composition of the aryl three arm silane that contain urea groups, amino and the aryl four arm silane that contain urea groups.
Embodiment 24
0.35mol (71.85g) isocyanic ester propyl trimethoxy silicane is dissolved in 200mL methylene dichloride, stand-by; Again by 1 of 0.1mol (12.32g), 3,5-triaminobenzene adds in the four-hole round-bottomed flask that dropping funnel, agitator and thermometer are housed, logical nitrogen, stirs, and dropwise adds the dichloromethane solution of above-mentioned isocyanic ester propyl trimethoxy silicane, keep 10 ℃ of reaction 2h of temperature of reaction, temperature increase to 35 ℃ continues reaction 2h afterwards, and the part methylene chloride as solvent is removed in distillation, obtains target compound-(I-1) and the composition solution of isocyanic ester propyl trimethoxy silicane.
Embodiment 25
0.45mol (92.38g) isocyanic ester propyl trimethoxy silicane is dissolved in 300mL methylene dichloride, stand-by; Again by 3 of 0.1mol (21.43g), 3 ', 4,4 '-biphenyl tetramine adds in the four-hole round-bottomed flask that dropping funnel, agitator and thermometer are housed, logical nitrogen, stir, the dichloromethane solution that dropwise adds above-mentioned isocyanic ester propyl trimethoxy silicane, keep 10 ℃ of reaction 2h of temperature of reaction, temperature increase to 40 ℃ continues reaction 3h afterwards, the part methylene chloride as solvent is removed in distillation, obtains the composition solution of above-mentioned target compound-(III-1) and isocyanic ester propyl trimethoxy silicane.
Embodiment 26~30
With isocyanic ester propyl-triethoxysilicane, isocyanic ester isopropylidene Trimethoxy silane, isocyanic ester sec.-propyl triethoxyl silane, isocyanic ester propyl chloride methyl dimethoxysilane, isocyanic ester propyl chloride methyldiethoxysilane, replace isocyanic ester Trimethoxy silane respectively, all the other conditions are with embodiment 24.
Embodiment 31~35
With isocyanic ester propyl-triethoxysilicane, isocyanic ester sec.-propyl Trimethoxy silane, isocyanic ester sec.-propyl triethoxyl silane, isocyanic ester propyl chloride methyl dimethoxysilane, isocyanic ester propyl chloride methyldiethoxysilane, replace isocyanic ester Trimethoxy silane respectively, all the other conditions are with embodiment 25.