CN101497252A - Polymer brush structure of polymer-based composite material interface as well as method and application for building the same - Google Patents
Polymer brush structure of polymer-based composite material interface as well as method and application for building the same Download PDFInfo
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- CN101497252A CN101497252A CNA2009100471808A CN200910047180A CN101497252A CN 101497252 A CN101497252 A CN 101497252A CN A2009100471808 A CNA2009100471808 A CN A2009100471808A CN 200910047180 A CN200910047180 A CN 200910047180A CN 101497252 A CN101497252 A CN 101497252A
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Abstract
The invention relates to a polymer brush structure on interface of a polymer matrix composite material and a construction method and application thereof. The invention adopts a triblock copolymer with a specific structure to process a reinforced material, and silicon hydroxide radical formed after the hydrolysis of the copolymer and the reinforced material form chemical bond combination and other strong interactions. In the composite process of the reinforced material and a polymeric matrix, block molecule chains in the copolymer having better compatibility with the polymeric matrix enter matrix by diffusion and form a mutually-snarled or interlocked structure with matrix molecule chains. Middle flexible blocks of the copolymer deposit on the surface of the reinforced material and form interface flexible layers, so the polymer brush structure is formed on the interface of the composite material. With the polymer brush structure, the reinforced material and the matrix form firm interface bonding, and the interface flexible layers formed by the middle flexible blocks can relieve the stress concentration, relax the heat stress, absorb externally-applied impact energy and crack extension energy in a large amount, and effectively improve the strength and the toughness of the polymer matrix composite material.
Description
Technical field
The present invention relates to a kind of brush structure of polymer and construction method thereof and application, especially the brush structure of polymer at polymer matrix composite interface and construction method thereof and application.
Background technology
The interface is the important micro-structural of composite, and the structure and the performance at interface have determined performance of composites.Make the fortifying fibre in the composite give full play to humidification, must between fiber and resin matrix, form effective interface bonding.Inorganic reinforcing material and the compatibility between polymer, compatibility are generally relatively poor, generally are difficult to form effective bonding, and fiber can't be given full play to the effect of its enhancing, and the mechanical property of composite is relatively poor.By physics, chemical modification methods such as (but introducing reactive activity group) to the surface modification (as methods such as etching, surface grafting, coupling agent treatment, surface-coated) of fiber and resin matrix, can improve the wetability between fiber and matrix, even between fiber and matrix, form chemical bond and combine, can improve the interface binding intensity between fiber and matrix effectively, help improving the intensity and the modulus of composite.But cross the decline that strong interface bonding can cause composite impact flexibility, in order to obtain impact flexibility composite preferably, the sacrificial section of having to intensity and modulus, the interface bonding of design appropriateness.
There is the stress concentration phenomenon in the fibre-reinforced polymer composites, there is bigger difference in thermophysical property between reinforcing material and resin matrix, in Composite Preparation, moulding and storage process because variation of temperature, can form thermal stress at the interface, will the ability of interface transmitted load had a negative impact.Meso-mechanical analysis is thought, introduces flexible layer at the interface, can make the interface toughness of transmitted load, concentrated, the lax interface residual stress of minimizing stress, raising composite equably.The foreign scholar
[1～6]Coat the thermoplastic polymer that elastomeric flexible-chain polymer of one deck or modulus and glass transition temperature are lower than matrix resin at fiber surface by methods such as polymerization and coatings, under the situation that hope does not have significantly to descend in intensity, modulus, improve the erosion-resisting characteristics of composite largely, domestic also have the scholar to carry out similar research.The inventor in the grafting of fiberglass surfacing and crosslinked, has introduced the interface flexible layer by rubber molecular chain in glass fiber reinforced polypropylene composite material, obtained the higher composite of toughness.As document: [
1] Mohammad M.Ranjbaran, Bamin Khomami., Polymer Engineeringand Science, 1996,36:1875-1885.[
2] Pegoretti A, Accorsi M.L., Dibenedetto A.T., Journal ofMaterials Science, 1996,31:6145-6153.[
3] Tillie M.N., Lam T.M., Gerard J.F., CompositesScience and Technology, 1998,58:659-663.[
4] Pegoretti A., Fidanza M., Migliaresi C., DibenedettoA.T., Composites, Part A:Applied Science and Manufacturing, 1998,29:283-291.[
5] Labronici M., Zshida H., Composite Interfaces, 1998,5:257-275.[
6] Rohchoon Park, Jyongsik Jang, CompositesScience and Technology, 1998,58:979-985.
But the character of this class boundary layer and the process conditions of introducing thereof have very big influence to interface bond strength, and the flexible layer of introducing is difficult to form good bonding with matrix polymer, and interface shear strength is lower, and the strength of materials and modulus all have decline in various degree.How obtaining the interfacial structure of high strength, high tenacity, is the key that balancing performances such as composite material strength, modulus and toughness are improved, and being still domestic and international composite researcher needs the further problem of solution.
The inventor has synthesized a kind of random copolymer macromolecular coupling agent (CN 1298890 A), adopt this coupling agent that surface treatment is carried out in inorganic filler (mica, calcium carbonate, talcum powder, wollastonite, glass microballoon), improved the mechanical property of filler filling polypropylene composite material to a certain extent.But be confined to the molecular characterization of random copolymer, the interaction between coupling agent and the polymeric matrix and the interfacial structure of formation await further enhancing by being out of shape endergonic ability.
The inventor also by the anionic polymerisation controlledly synthesis a kind of block copolymer, as the disclosed technology of CN1446834A patent, adopt the copolymer that is synthesized that mica, wollastonite, wood powder, glass microballoon are carried out modification, improved intensity, modulus and the toughness of modified filler and polypropylene, poly styrene composite material effectively; After glass fibre that the synthetic copolymer of employing is handled and polystyrene are compound, also can improve the interface binding intensity of composite to a certain extent.
Summary of the invention
The present invention discloses brush structure of polymer and the construction method and the application in the Composite Preparation process at a kind of polymer matrix composite interface, by constructing brush structure of polymer at composite material interface, overcome the deficiency that poor toughness and intensity in the prior art, modulus descend, for the exploitation of high strength, high rigidity, high-ductility polymer based composites provides enhancings, toughness reinforcing interface to design new method.
Technical conceive:
Design and synthesize the controlled triblock copolymer of a class formation, adopt this copolymer to handle reinforcing material, copolymer by silane coupler block hydrolysis wherein after silicon hydroxyl that forms and strong interactions such as reinforcing material formation chemical bond combines.In the recombination process of reinforcing material and polymeric matrix, assemble with the block copolymer of reinforcing material formation strong interaction, the block A stretching, extension good with the resin matrix compatibility enters in the matrix, form " bristle ", the soft segment B of copolymer is at the reinforcing material surface deposition, form the interface flexible layer, thereby form " polymer brush " structure at the interface of composite.In this brush structure of polymer, " bristle " modes such as curing reaction by forming mutual entanglement or interlocking structure and participate in matrix with the substrate molecule chain form strong interaction with matrix, form firm interface bonding between reinforcing material and matrix; But the formed interface of middle flexible blocks B flexible layer relieve stresses is concentrated, lax thermal stress, absorb applied shock energy and crack propagation energy in a large number, thereby obtains the interfacial structure of high strength, high tenacity in composite.
Technical scheme:
Ternary block polymer of the present invention, its structure fragment is as follows :-(A) n
1-(B) n
2-(C) n
3-, block A is a polystyrene; B block selects with the matrix compatibility poor slightly and vitrification point to be lower than the soft segment of room temperature, can adopt to comprise a kind of in butyl polyacrylate, the polyacrylic acid tert-butyl ester etc.; Block C is for forming the block of strong interaction with reinforcing material, the silane coupler for the two keys of band commonly used.N1 is the degree of polymerization of block A, and it is worth between 50～300; N2 is the degree of polymerization of B block, and it is worth between 50～150; N3 is the degree of polymerization of block C, and it is worth between 1～22.
The copolymer of project organization adopts the controlledly synthesis of ATRP (ATRP) method, addition by regulating initator, monomer and proportioning etc., the structure that can strict control block copolymer and the length of each block.
The polymer of said structure is to adopt following steps synthetic:
(1) n of A block-(A)
1-synthetic
Adopt atom transfer radical polymerization method, the monomer styrene, part, metal halide and the initator that add quantitative A block in the there-necked flask, stir and feed nitrogen, slowly be warming up to 75 ℃～90 ℃, behind insulation reaction 5～8h,, in absolute methanol, precipitate with the oxolane dissolving, vacuum drying obtains product and is the n of the A block of C-Br key end group-(A)
1-Br.
(2) n of A, B diblock copolymer-(A)
1-(B) n
2-synthetic
In the there-necked flask under the nitrogen protection, add certain proportioning solvent, B block monomer, part, metal halide and C-Br key end group-(A) n
1-Br polymerization initiator stops reaction behind 40 ℃～120 ℃ stirring 4～40h.Purifying, separating step be with (1), and obtaining with the C-Br key is the n of A, B diblock copolymer-(A) of end group
1-(B) n
2-Br.
(3) n of A, B, C triblock copolymer-(A)
1-(B) n
2-(C) n
3-synthetic
With the C-Br key is the n of A, B diblock copolymer-(A) of end group
1-(B) n
2The monomer of-B, metal halide, part, solvent and C block places the there-necked flask of blanket of nitrogen in 40 ℃～120 ℃ reactions, and purification step is with (2), promptly obtains the n of triblock copolymer-(A)
1-(B) n
2-(C) n
3-.
The rate of charge of described part, catalyst and initator is: 1:1:1.
Described initator comprises that alpha-halogen thing, α-bromine (chlorine) are for vinylbenzene, ethyl;
Described metal halide comprises CuCl/CuBr or FeCl
2
Described part comprises N, N, N ', N ', N " five methyl diethylentriamine or 2-2 '-bipyridyl;
Described solvent comprises a kind of in dimethylbenzene, toluene, benzene, acetone, cyclohexanone or the dimethyl formamide.
Block copolymer is to the surface treatment of reinforcing material and the formation of both strong interactions thereof:
The block polymer that is synthesized is placed xylene solvent, the aqueous acetic acid of adding pH4～5 makes the silane coupler block generation hydrolysis in the block polymer, formation can form the silicon hydroxyl of strong interaction with reinforcing material, the concentration of control block copolymer is 0.1%～2%wt%, stir 0.5～2h and form uniform and stable dispersion, as inorganic agent to reinforcing material, also can with the inorganic agent of the paired reinforcing material of other auxiliary agent mutual group.Adopt this inorganic agent to soak or the coating reinforcing material, place 30min in room temperature and remove unnecessary inorganic agent, place 80 ℃ of environment, remove decentralized medium such as solvent, water and make the coupling agent block and the reinforcing material surface reacts, be warming up to 120 ℃ behind the 90min and continue reaction 30min, block copolymer forms strong interactions such as chemical bond combines by the silicon hydroxyl of coupling agent block with the reinforcing material surface.
Described reinforcing material comprises glass (fiber, microballon), basalt fibre, mica, wollastonite, talcum powder etc.
Compound and the block copolymer of reinforcing material and resin is in the assembling at interface:
(1) reinforcing material and thermoplastic resin are compound
The reinforcing material of handling through block copolymer contacts under pressure with the thermoplastic resin of molten condition, the viscosity of melt of thermoplastic polymers is higher usually, suitably improve the temperature of polymer melt, help reducing its viscosity, promote it closely to contact and form good wetting with glass fibre, combined temp is higher 30～80 ℃ than its melting temperature usually.Reinforcing material and resin interact, the polystyrene segment (block A) that forms in the block copolymer of strong interaction with reinforcing material surface has good compatibility with matrix resin, enter in the matrix by diffusion block A strand and to become strand to tangle mutually or interlocking structure with resin-shaped, flexible blocks B then forms the interface flexible layer in the reinforcing material surface deposition.
(2) reinforcing material and thermosetting resin (unsaturated polyester (UP), vinylite etc.) are compound
Resin is mixed by certain proportioning with curing agent, curing accelerator etc., mix the formation glue, will mix with glue, obtain glass fibre reinforced composion sheet material after the curing through the reinforcing material that block copolymer was handled.Reinforcing material is with after glue contacts, the polystyrene segment (block A) that forms in the block copolymer of strong interaction with reinforcing material surface has good compatibility (unsaturated polyester (UP), vinylite are diluent with styrene) with matrix resin, enter in the matrix by diffusion block A strand and to become strand to tangle mutually or interlocking structure with resin-shaped, flexible blocks B then forms the interface flexible layer in the reinforcing material surface deposition.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is the infrared spectrogram of PS-b-PnBA-b-MPS.
Fig. 2 is the nmr spectrum of PS-b-PnBA-b-PMPS.
Fig. 3 is glass surface total reflection infrared spectrogram after the long-term drip washing of solvent that block copolymer is handled.
Fig. 4 is that block copolymer-modified glass fibre (a) and surface coat behind the matrix polystyrene DSC curve of (b) back (c) before the fusion.
Fig. 5 is that the AFM after compound schemes the silicon chip surface handled of triblock copolymer with polystyrene.
The reference numeral explanation:
Among Fig. 1, spectrogram transverse axis Wavenumber is a wave number, and longitudinal axis Transmittance is a light transmittance.
Among Fig. 3, spectrogram transverse axis Wavenumber is a wave number, and longitudinal axis Transmittance is a light transmittance.
Among Fig. 4, DSC curve transverse axis T emperature is a temperature, and longitudinal axis Heatflow is a heat content.
The specific embodiment
(1) styrene/acrylic butyl ester/gamma-methyl allyl acyloxypropyl trimethoxysilane triblock copolymer is synthetic
1. synthesizing of big molecule styrene initator
In the 250ml of blanket of nitrogen there-necked flask, add 50ml styrene successively, 0.913ml N, N, N ', N ', " five methyl diethylentriamine; 0.626g Catalysts Cu Br stirs 30min and makes mixture become homogeneous phase N, injects 0.65ml initator bromobenzyl with syringe then; stir and be warming up to 90 ℃ of reactions cooling cooling after 8 hours; stop reaction, add the 120ml oxolane and make the product dissolving, product is crossed Al
2O
3Post is with adsoption catalyst and remove copper ion, and solution joins in the absolute methanol solvent, has sediment to separate out, and suction filtration obtains the big molecule styrene initator that sediment is a C-Br key end group.
2. styrene/acrylic butyl ester diblock copolymer is synthetic
In the 250ml of blanket of nitrogen there-necked flask, add big molecule styrene initator, 0.11g Catalysts Cu Br, 10ml butyl acrylate and 25ml acetone that 6.89g is synthesized in 1. successively, add 0.15ml ligand N after stirring 30min, N, N ', N ', " five methyl diethylentriamine is warming up to 110 ℃ of reactions 27 hours; add tetrahydrofuran solvent in product, mixture is crossed Al to N
2O
3Post is with adsoption catalyst and remove copper ion, and solution joins in the absolute methanol solvent, has sediment to separate out, and the sediment that suction filtration separates obtains the styrene/acrylic butyl ester diblock copolymer with the C-Br end group through 60 ℃ of vacuum drying 24 hours;
3. styrene/acrylic butyl ester/gamma-methyl allyl acyloxypropyl trimethoxysilane triblock copolymer is synthetic
In the 250ml of blanket of nitrogen there-necked flask, add 25ml dimethylbenzene successively, 7.88g the styrene/acrylic butyl ester diblock copolymer of the band C-Br end group that is synthesized 2., be stirred to dissolving fully, add 0.11g Catalysts Cu Br, 4ml gamma-methyl allyl acyloxypropyl trimethoxysilane again, add 0.16ml ligand N behind the stirring 30min, N, " five methyl diethylentriamine; be warming up to 120 ℃ then stops reaction after under agitation reacting 24h for N ', N ', N.Add tetrahydrofuran solvent in product, mixture is crossed Al
2O
3Post is with adsoption catalyst and remove copper ion, solution joins in the absolute methanol solvent, have sediment to separate out, the sediment that suction filtration separates obtains styrene/acrylic butyl ester/gamma-methyl allyl acyloxypropyl trimethoxysilane triblock copolymer through 60 ℃ of vacuum drying 24 hours.
Styrene/acrylic butyl ester/gamma-methyl allyl acyloxypropyl trimethoxysilane triblock copolymer infrared spectrum is seen accompanying drawing 1, and nuclear magnetic spectrogram is seen accompanying drawing 2.With reference to the accompanying drawings in 1 the infrared spectrogram of polymer as can be known, 3012cm
-1Near absworption peak is the stretching vibration of the C-H on the phenyl ring in the polymer, 1731cm
-1Absworption peak be the ester group of butyl acrylate, 1033cm
-1Characteristic absorption peak for the silane coupler siloxy.From accompanying drawing 2 nuclear magnetic spectrograms as can be known, about 7ppm is the characteristic absorption peak of phenyl ring, and each peak that influences that each alkyl of St, BA and MPS is subjected to carbonyl or phenyl ring is distributed in 0.95ppm between the 4.22ppm.In conjunction with the characteristics of the atom transition free radical polymerization reaction that is adopted, confirm that product is designed molecular structure.The number-average molecular weight of synthetic block copolymer is determined as 20700 through gel chromatography (GPC), and molecular weight distributing index is 1.267, and block is than being 101.20:41.93:18.78.
(2) block copolymer is to the surface treatment of glass fibre
With commercially available non-twist fibre glass roving, place 500 ℃, the Muffle furnace 6h of air atmosphere, remove the original size of fiber surface.Getting triblock polymer synthetic among the 2.5g (1) joins in the 280ml xylene solvent, acetic acid (HAC) aqueous solution that splashes into 10ml pH4～5 makes the silane coupler hydrolysis in the block copolymer, control triblock polymer concentration is 1wt%, stir 1h with dissolving fully, with this mixed liquor glass fibre is carried out surface-coated, 30min is placed in 80 ℃ of environment, remove solvent, decentralized media such as water also make the coupling agent block and the reinforcing material surface reacts, be warming up to 120 ℃ behind the 90min and continue reaction 30min, glass fibre and block copolymerization compound coupling agent have formed strong interaction.
After 48 hours, measure its surperficial total reflection infrared spectrum such as Fig. 3 through tetrahydrofuran solvent drip washing through the glass that block copolymer is handled, the result of Fig. 3 shows that block copolymer and glass surface have formed strong interaction.
(3) glass fibre and polystyrene is compound
Polystyrene resin places crucible, be heated to electric furnace and make the resin fusion and to make melt temperature reach 220 ℃, will be dipped in the polystyrene melt, take out behind the 5min through the glass fibre that handled step (2), in 250 ℃ oven 10min, be cooled under the room temperature and solidify.
Measure the DSC curve (Fig. 4) of compound system, the variation of the glass transition temperature of matrix and each block of copolymer shows in recombination process in the system, and the block A strand compatible with matrix diffuses into matrix and form than strong interaction with matrix.
After silicon chip surface that the section copolymer is handled is compound with polystyrene, adopt atomic force microscope observation to form (Fig. 5) show that the flexible blocks of copolymer is at reinforcing material surface aggregation formation flexible layer.
The interface shear strength mean value that adopts the little unsticking method of monofilament to measure styrafil sees Table 1.
| Composite | Interface shear strength (MPa) |
| |
14.9 |
| |
17.7 |
| |
11.8 |
| Comparative Examples 1 | 3.9 |
| Comparative Examples 2 | 5.5 |
Table 1
Example 2
(1) styrene/acrylic butyl ester/gamma-methyl allyl acyloxypropyl trimethoxysilane triblock copolymer is synthetic
1. synthesizing of big molecule styrene initator
N, N, N ', N ', N " five methyl diethylentriamine is 0.456ml, Catalysts Cu Br 0.313g, initator bromobenzyl 0.32ml, other is with example 1.
2. styrene/acrylic butyl ester diblock copolymer is synthetic
In the 250ml of blanket of nitrogen there-necked flask, add big molecule styrene initator, 0.20g Catalysts Cu Br, 10ml butyl acrylate and 25ml acetone that 30.24g is synthesized in 1. successively, add 0.29ml ligand N after stirring 30min, N, N ', N ', " five methyl diethylentriamine, other is with example 1 for N.
3. styrene/acrylic butyl ester/gamma-methyl allyl acyloxypropyl trimethoxysilane triblock copolymer is synthetic
In the 250ml of blanket of nitrogen there-necked flask, add 25ml dimethylbenzene successively, 21.97g the styrene/acrylic butyl ester diblock copolymer of the band C-Br end group that is synthesized 2., be stirred to dissolving fully, add 0.11g Catalysts Cu Br, 4ml gamma-methyl allyl acyloxypropyl trimethoxysilane again, add 0.16ml ligand N behind the stirring 30min, N, " five methyl diethylentriamine; be warming up to 120 ℃ then stops reaction after under agitation reacting 24h for N ', N ', N.Other is with example 1.
Measuring actual block ratio is: 207.78:45.45:9.76, M
n=29950, M
W/ M
n=1.202.
(2) block copolymer is to the surface treatment of glass fibre
With example 1.
(3) glass fibre and polystyrene is compound
With example 1.
Example 3
(1) styrene/acrylic butyl ester/gamma-methyl allyl acyloxypropyl trimethoxysilane triblock copolymer is synthetic
1. synthesizing of big molecule styrene initator
With example 2.
2. styrene/acrylic butyl ester diblock copolymer is synthetic
Ligand N, " the five methyl diethylentriamine consumption is 0.30ml, and other is with example 2 for N, N ', N ', N.
3. styrene/acrylic butyl ester/gamma-methyl allyl acyloxypropyl trimethoxysilane triblock copolymer is synthetic
In the 250ml of blanket of nitrogen there-necked flask, add 25ml dimethylbenzene successively, 26.15g the styrene/acrylic butyl ester diblock copolymer of the band C-Br end group that is synthesized 2., be stirred to dissolving fully, add 0.11g Catalysts Cu Br, 4ml gamma-methyl allyl acyloxypropyl trimethoxysilane again, add 0.16ml ligand N behind the stirring 30min, N, N ', N ', N " five methyl diethylentriamine; be warming up to 120 ℃ then, other is with example 2.
Measuring actual block ratio is: 2297.55:45.69:18.15, Mn=41470, M
W/ M
n=1.915.
(2) block copolymer is to the surface treatment of glass fibre
With example 1.
(3) glass fibre and polystyrene is compound
With example 1.
Example 4
By tert-butyl acrylate instead of propylene acid butyl ester, other is with example 1.
Example 5
By basalt fibre instead of glass fiber, other is with example 1.
Comparative Examples 1
After glass fibre is removed the surface infiltration agent, do not adopt block polymer to handle, compound with polystyrene, combination process is with example 1, and the interface shear strength mean value that adopts the little unsticking method of monofilament to measure styrafil sees Table 1.
Comparative Examples 2
After glass fibre is removed the surface infiltration agent, adopt little molecule KH-570 coupling agent (gamma-methyl allyl acyloxypropyl trimethoxysilane, MPS) glass fabric is carried out surface treatment, surface treatment process is: the mixed liquor of preparation 0.5wt%KH-570 coupling agent and deionized water, the pH value that adopts commercially available acetate to regulate mixed liquor is 4, stir 30min and form uniform solution, the glass fibre immersion is taken out behind the 10min in this solution, drain the coupling agent solution of filling in glass cloth under the room temperature, under 80 ℃, handle 90min then, be warming up to 120 ℃ again and handle 30min., compound with polystyrene, combination process is with example 1, and the interface shear strength mean value that adopts the little unsticking method of monofilament to measure styrafil sees Table 1.
(1) styrene/acrylic butyl ester/gamma-methyl allyl acyloxypropyl trimethoxysilane triblock copolymer is synthetic
With embodiment 1.
(2) block copolymer is to the surface treatment of glass fabric
With commercially available glass fabric, place 500 ℃, the Muffle furnace 6h of air atmosphere, remove the original size of fiber surface.Getting triblock polymer synthetic among the 5.0g (1) joins in the 560ml xylene solvent, acetic acid (HAC) aqueous solution that splashes into 10ml pH4～5 makes the silane coupler hydrolysis in the block copolymer, control triblock polymer concentration is 1wt%, stir 1h with dissolving fully, with this mixed liquor glass fibre is carried out surface-coated, 30min is placed in 80 ℃ of environment, remove solvent, decentralized media such as water also make the coupling agent block and the reinforcing material surface reacts, be warming up to 120 ℃ behind the 90min and continue reaction 30min, glass fibre and block copolymerization compound coupling agent form strong interaction.
(3) glass fiber reinforcement unsaturated polyester Composite Preparation
After 100 parts of unsaturated polyester resins and 0.2 part of cobalt octoate liquid mixed, drip 1 part of methyl ethyl ketone peroxide again, fully stir and discharge bubble, be mixed with glue.Then treated glass fabric is put into successively the glue dipping for preparing after half an hour in layer put into flat plate mold, under the pressure of 1MPa, do thick sheet material, be processed into bending and notched impact specimen according to the ASTM standard respectively into about 4mm through cold curing.Adopt the ASTM standard mechanical property of glass fiber reinforcement unsaturated polyester composite to be tested result such as table 2.
Table 2
| Composite | Bending strength (MPa) | Bending modulus (MPa) | Notched izod impact strength (kJ/m2) |
| |
139.6 | 11545 | 13.4 |
| Embodiment 6 | 143.4 | 12197 | 12.7 |
| |
137.1 | 12023 | 13.3 |
| Comparative Examples 3 | 96.9 | 7752 | 8.0 |
| Comparative Examples 4 | 102.6 | 9998 | 8.1 |
Embodiment 6
Synthesizing of styrene/acrylic butyl ester/gamma-methyl allyl acyloxypropyl trimethoxysilane triblock copolymer with embodiment 2.Other is with embodiment 5.
Synthesizing of styrene/acrylic butyl ester/gamma-methyl allyl acyloxypropyl trimethoxysilane triblock copolymer with embodiment 3.Other is with embodiment 5.
Comparative Examples 3
Commercially available glass fabric is cooled to room temperature after removing surface infiltration agent (placing 6h in the Muffle furnace of 500 ℃ of air atmosphere), directly and unsaturated polyester (UP) compound, recombination process is with example 5.
Comparative Examples 4
Commercially available glass fabric is after removing surface infiltration agent (placing 6h in the Muffle furnace of 500 ℃ of air atmosphere), be cooled to room temperature, adopt little molecule KH-570 coupling agent (gamma-methyl allyl acyloxypropyl trimethoxysilane, MPS) glass fabric is carried out surface treatment, surface treatment process is: the mixed liquor of preparation 0.5wt%KH-570 coupling agent and deionized water, the pH value that adopts commercially available acetate to regulate mixed liquor is 4, stir 30min and form uniform solution, glass fabric is immersed in this solution takes out behind the 10min, drain the coupling agent solution of filling in glass cloth under the room temperature, under 80 ℃, handle 90min then, be warming up to 120 ℃ again and handle 30min.
Glass fabric is identical with embodiment 5 with enhancing unsaturated polyester (UP) recombination process.
Compound resin matrix is acrylonitrile/butadiene/styrene copolymer (ABS), and other is with example 1.
Compound resin matrix is acrylonitrile/styrol copolymer (SAN), and other is with example 1.
Only for the preferred embodiment of invention, be not to be used for limiting practical range of the present invention in sum.Be that all equivalences of doing according to the content of the present patent application claim change and modification, all should be technology category of the present invention.
Claims (10)
1, the brush structure of polymer at a kind of polymer matrix composite interface, it is characterized in that: this structure comprises matrix, triblock copolymer and reinforcing material, triblock copolymer block C forms chemical bond with reinforcing material and combines, triblock copolymer block A extends into matrix, form " bristle ", the soft segment B of copolymer forms the interface flexible layer at the reinforcing material surface deposition.
2, according to right described 1 described brush structure of polymer, it is characterized in that: described triblock copolymer, its structure fragment is as follows :-(A) n
1-(B) n
2-(C) n
3-, block A is a polystyrene; B block is the monomer that comprises butyl polyacrylate, the polyacrylic acid tert-butyl ester; Block C is the silane coupler of the two keys of band; N1 is the degree of polymerization of block A, and it is worth between 50～300; N2 is the degree of polymerization of B block, and it is worth between 50～150; N3 is the degree of polymerization of block C, and it is worth between 1～22.
3, according to right described 2 described brush structure of polymer, it is characterized in that: the preparation method of described triblock copolymer may further comprise the steps:
The n of step 1 A block-(A)
1-synthetic:
Adopt atom transfer radical polymerization method, the monomer styrene, part, metal halide and the initator that add quantitative A block in the there-necked flask, stir and feed nitrogen, slowly be warming up to 75 ℃～90 ℃, behind insulation reaction 5～8h,, in absolute methanol, precipitate with the oxolane dissolving, vacuum drying obtains product and is the n of the A block of C-Br key end group-(A)
1-Br;
The n of step 2 A, B diblock copolymer-(A)
1-(B) n
2-synthetic:
In the there-necked flask under the nitrogen protection, add certain proportioning solvent, B block monomer, part, metal halide and C-Br key end group-(A) n
1-Br polymerization initiator, 40 ℃～120 ℃ stop reaction after stirring 4～40h, and purifying, separating step be with step 1, and obtaining with the C-Br key is the n of A, B diblock copolymer-(A) of end group
1-(B) n
2-Br;
The n of step 3:A, B, C triblock copolymer-(A)
1-(B) n
2-(C) n
3-synthetic:
With the C-Br key is the n of A, B diblock copolymer-(A) of end group
1-(B) n
2The monomer of-B, metal halide, part, solvent and C block places the there-necked flask of blanket of nitrogen in 40 ℃～120 ℃ reactions, and purification step is with step 2, promptly obtains the n of triblock copolymer-(A)
1-(B) n
2-(C) n
3-.
4, brush structure of polymer according to claim 3 is characterized in that: the rate of charge of described part, catalyst and initator is: 1:1:1.
5, brush structure of polymer according to claim 3 is characterized in that: described initator comprises that alpha-halogen thing, α-bromine (chlorine) are for vinylbenzene, ethyl.
6, brush structure of polymer according to claim 3 is characterized in that: described metal halide comprises CuCl/CuBr or FeCl
2
7, brush structure of polymer according to claim 3 is characterized in that: described part comprises N, N, N ', N ', N " five methyl diethylentriamine or 2-2 '-bipyridyl.
8, brush structure of polymer according to claim 3 is characterized in that: described solvent comprises a kind of in dimethylbenzene, toluene, benzene, acetone, cyclohexanone or the dimethyl formamide.
9, according to the construction method of right described 1 or 2 described brush structure of polymer, it is characterized in that may further comprise the steps:
Step 1 triblock polymer is handled the reinforcing material surface, forms strong interaction:
Triblock polymer is placed xylene solvent, the aqueous acetic acid that adds pH4～5, the concentration of block copolymer is 0.1%～2%wt%, stir 0.5～2h and form uniform and stable dispersion, adopt this inorganic agent to soak or the coating reinforcing material, place 30min in room temperature and remove unnecessary inorganic agent, place 80 ℃ of environment, remove decentralized medium such as solvent, water and make the coupling agent block, be warming up to 120 ℃ behind the 90min and continue to react 30min with the reinforcing material surface reacts.
Step 2 reinforcing material and matrix material are compound:
A) when matrix material be thermoplastic resin: the reinforcing material of handling through block copolymer contacts under pressure with the thermoplastic resin of molten condition, and this combined temp is higher 30～80 ℃ than its melting temperature;
B) when matrix material be thermosetting resin: resin is mixed by certain proportioning with curing agent, curing accelerator etc., mix the formation glue, to mix with glue through the reinforcing material that block copolymer was handled, obtain glass fibre reinforced composion sheet material after the curing.
10, according to arbitrary described brush structure of polymer of the described 1-8 of right or construction method according to claim 9, it is characterized in that: described reinforcing material comprises glass (fiber, microballon), basalt fibre, mica, wollastonite, talcum powder.
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| CN102603362A (en) * | 2012-01-20 | 2012-07-25 | 中国科学院长春应用化学研究所 | Preparation method of block polymer brush |
| CN102875195A (en) * | 2012-09-20 | 2013-01-16 | 华东理工大学 | Method for preparing polymer brush films with multiple stimulation responses |
| CN103906776A (en) * | 2011-07-19 | 2014-07-02 | 表面创新有限公司 | Polymeric structure |
| CN105601129A (en) * | 2015-12-23 | 2016-05-25 | 晏玲莉 | Reinforced soakage agent for basalt fibers |
| CN107749293A (en) * | 2017-09-12 | 2018-03-02 | 滁州远方车船装备工程有限公司 | A kind of broad band sound absorption glued board with interlayer structure and preparation method thereof |
| CN111542550A (en) * | 2017-12-28 | 2020-08-14 | 国立研究开发法人产业技术综合研究所 | Base for forming polymer brush, method for producing the base, and precursor liquid used in the method |
| CN113354783A (en) * | 2020-03-05 | 2021-09-07 | 中国科学院化学研究所 | Toughened thermoplastic material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103906776A (en) * | 2011-07-19 | 2014-07-02 | 表面创新有限公司 | Polymeric structure |
| CN102603362A (en) * | 2012-01-20 | 2012-07-25 | 中国科学院长春应用化学研究所 | Preparation method of block polymer brush |
| CN102603362B (en) * | 2012-01-20 | 2013-12-11 | 中国科学院长春应用化学研究所 | Preparation method of block polymer brush |
| CN102875195A (en) * | 2012-09-20 | 2013-01-16 | 华东理工大学 | Method for preparing polymer brush films with multiple stimulation responses |
| CN102875195B (en) * | 2012-09-20 | 2014-03-12 | 华东理工大学 | Method for preparing polymer brush films with multiple stimulation responses |
| CN105601129A (en) * | 2015-12-23 | 2016-05-25 | 晏玲莉 | Reinforced soakage agent for basalt fibers |
| CN107749293A (en) * | 2017-09-12 | 2018-03-02 | 滁州远方车船装备工程有限公司 | A kind of broad band sound absorption glued board with interlayer structure and preparation method thereof |
| CN111542550A (en) * | 2017-12-28 | 2020-08-14 | 国立研究开发法人产业技术综合研究所 | Base for forming polymer brush, method for producing the base, and precursor liquid used in the method |
| CN111542550B (en) * | 2017-12-28 | 2022-07-19 | 国立研究开发法人产业技术综合研究所 | Base for forming polymer brush, method for producing the base, and precursor liquid used in the method |
| CN113354783A (en) * | 2020-03-05 | 2021-09-07 | 中国科学院化学研究所 | Toughened thermoplastic material and preparation method and application thereof |
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