CN1187836A - Phenolic resin compositions with improved impact resistance - Google Patents
Phenolic resin compositions with improved impact resistance Download PDFInfo
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- CN1187836A CN1187836A CN96194806A CN96194806A CN1187836A CN 1187836 A CN1187836 A CN 1187836A CN 96194806 A CN96194806 A CN 96194806A CN 96194806 A CN96194806 A CN 96194806A CN 1187836 A CN1187836 A CN 1187836A
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Abstract
Phenolic siloxane composition are prepared by 1) combining phenol with an aldehyde and an alkoxy or silanol-functional silicone intermediate, 2) combining a phenolic novolac resin with a formaldehyde donor and an alkoxy or silanol-functional silicone intermediate or 3) combining a phenolic resole resin with an alkoxy or silanol-functional silicone intermediate. Catalysts to facilitate the formation of a phenolic resin, the condensation of the phenolic resin and the hydrolysis and/or condensation of the silicone intermediate can optionally be added. The resulting composition comprises an IPN of siloxane polymers and phenolic polymers and has flame, heat and chemical resistance equal to or exceeding conventional phenolic resins and improved impact resistance, tensile strength, flexural modulus and density.
Description
The field of the invention
The present invention relates generally to phenol resin composition, and said composition can provide resistivity against fire in many application scenarios, and the amount of being fuming is low and toxicity cigarette is low, thermotolerance, chemical proofing and good wear resistance simultaneously.Particularly, the present invention relates to silicone-modified phenol resin composition, said composition is except that having splendid performance such as above-described fire-resistant, heat-resisting, the shock strength and the toughness that also have improvement, improve overdo after retained strength, the rebound resilience of the phenol formaldehyde foam of modulus in flexure of improving and improvement.
Background of the present invention
Resol is the most ancient synthetic materials, is in early days to carry out catalyzed reaction by phenol and formaldehyde to make.Resol generally is heat cured (but being not so absolute), and have splendid thermotolerance, flame retardant resistance and a chemical proofing, have good electrical properties, good moisture resistance and antioxygen property, various matrix are had good adhesive power, and production cost is low.These performances make resol be widely used, bonding as timber and fiber, the abrasive material of agglutinating and coating, friction element, the binding agent of foundry's sand mo(u)ld and core, construction adhesive and contact adhesive, industry and decorative laminate, matrix material and moulding compound and coating, these only are several examples.
Although solidified resol has physicalies such as excellent heat-resisting, fire-retardant, chemical-resistant resistance, its natural characteristics is hard and crisp, and therefore, shock-resistance and snappiness are relatively poor.The resol that is made by base catalysis phenol formaldehyde (PF) reaction is that soluble phenolic resin is fragility, and its reason is the cross-linking density height, makes and all has high crosslink density in the whole polymer architecture because a large amount of methylols participate in hydroxymethylations.
This phenolic resin cured fragility and flexible shortage can not be used for it need be by the member of this resin formation or the application that is had certain snappiness and shock-resistance by the matrix of this resin-coating.Bear certain deflection or shock action coating the matrix of this type of resol can be because this type of bending or shock action cause brittle coating to come off and make matrix under the coating lose thermotolerance, flame resistivity and chemical proofing that protection and forfeiture are provided by coating.Recent decades, industrial sector improved the approach of phenol resin composition impact resistance always in searching.
Existing some kinds of methods can make with resol itself compares the phenol resin composition that snappiness makes moderate progress.An example is, adds wood powder, or other enhancement component and pigment and other additive are with the flexible mouldable heat-reactive phenolic resin composition that has been improved.But, this phenol resin composition adds these enhancement component and additive can reduce heat-resisting, anti-combustion and the chemical proofing that independent use resol is had in order to form.So the ability of obtaining the snappiness phenol resin composition according to aforesaid method has been represented compromise between improving of the reduction of thermotolerance, flame resistivity and chemical proofing and snappiness.Aforesaid method can't be used for the occasion that not only requires snappiness but also require fine heat-resisting, anti-combustion and chemical proofing.
It is by internal plasticization that another kind obtains the method for having improved flexible resol.In this method,, promptly add alcohol and carry out esterification as butanols with a part of methylol end-blocking.Preferentially pure and methylol reaction generates the butoxy side chain of resol.Adopt this method to reduce the resin functionality, thereby make the phenolic resin cured cross-linking density of gained reduce and improve snappiness.But the cost that obtains the snappiness improvement by this method is to have reduced phenolic resin cured heat-resisting, anti-combustion and the chemical proofing of gained.Therefore, this method can not be used to obtain the resol that existing snappiness has fine heat-resisting, anti-combustion and chemical proofing again.
In addition, be used to make moulding compound, the resol of laminate and matrix material often contains a large amount of water entrainments.Heating water evaporation during these resols forms micropore, thereby reduces the tensile strength and the modulus in flexure of gained solidified resol in cured article in solidification process, and makes the solidified resol more crisp and more lack snappiness.These micropores also cause the water absorbability of solidified resol to increase (by the porosity surface structure), and reduce chemical proofing.
Therefore, need a kind of phenol resin composition of preparation, said composition had not only had physicals such as good snappiness and shock-resistance but also had not reduced heat-resisting, anti-combustion of resol institute inherent and chemical proofing.Also need this phenol resin composition to have the water-retaining capacity of reduction in the preparation, thereby reduce the formation of micropore when solidifying.
Summary of the present invention
Therefore, in fact the present invention provides phenol resin composition, its preparation method is to use the polysiloxane intermediate of capacity to form the phenolic siloxane composition, and said composition has snappiness and the shock-resistance better than traditional phenol resin composition that does not contain siloxanes after solidifying.
First kind of embodiment of preparation phenolic siloxane composition is with the polysiloxane intermediate of phenol or fortified phenol and alkoxyl group or silanol-functional and the mixing of a kind of aldehyde.Second kind of embodiment is that the polysiloxane intermediate of a kind of novolac and alkoxyl group or silanol-functional and a kind of formaldehyde donor are mixed.The third embodiment is that a kind of resol is mixed with the polysiloxane intermediate of a kind of alkoxyl group or silanol-functional.Each component reaction in each embodiment generates the interpenetrating polymer networks of siloxane polymer and novolac polymer, and wherein novolac polymer comprises the Si-O group in its main chain.
In first kind of embodiment, use the catalyzer be selected from bronsted lowry acids and bases bronsted lowry promoting, or fortified phenol and aldehyde component form needed novolac or resol by phenol.If desired, can in first, second or the 3rd embodiment, use catalyzer to promote the condensation of newly-generated resol or resol raw material, catalyzer can comprise acid, alkali, and formaldehyde donor, this depends on that resol that is generated or the resol that is used as raw material are resol or novolac.
If desired, in the first, the second or the 3rd embodiment, can use the capacity catalyzer to promote hydrolysis and/or the condensation at low temperatures of polysiloxane intermediate.Catalyzer can comprise organometallic compound, amine compound and composition thereof.Preferred catalyzer is the mixture of a kind of organometallic compound and a kind of amine compound.
Phenol in first embodiment, aldehyde and polysiloxane intermediate; Novolac in second embodiment, formaldehyde donor and polysiloxane intermediate; Resol in the 3rd embodiment and polysiloxane intermediate; Be mixed together to form the phenolic siloxane composition with optional required catalyzer, said composition has than traditional performances such as the better shock-resistance of the phenol resin composition that does not contain siloxanes, tensile strength, modulus in flexure and density.In addition, this phenolic siloxane composition have with traditional phenol resin composition that does not contain siloxanes quite or better anti-combustion, heat-resisting and chemical proofing.Brief description of drawings
By the reference specification sheets, claims and accompanying drawing will have better understanding to the present invention, will understand above-mentioned and other characteristics and advantage of the present invention equally better, wherein:
Fig. 1 is the isometric view that comprises the long filament winding tube of the long filament of using the phenolic siloxane composition bond for preparing according to principle of the present invention;
Fig. 2 is an isometric view of using the long filament enhancing steel pipe of the phenolic siloxane composition bond for preparing according to principle of the present invention;
Fig. 3 is the cross-sectional side view that comprises the wood composite board of the phenolic siloxane composition bond agent for preparing by the principle of the invention;
Fig. 4 is that a slice comprises the foamy isometric view by the phenolic siloxane composition of principle of the invention preparation;
Fig. 5 a is the isometric view that comprises the brake belt material of the phenolic siloxane composition for preparing by the principle of the invention;
Fig. 5 b is the isometric view that comprises the clutch lining of the phenolic siloxane composition for preparing by the principle of the invention;
Fig. 6 is the isometric view that comprises the emery wheel of the phenolic siloxane composition for preparing by the principle of the invention.
Describe in detail
Generally speaking, phenolic siloxane composition of the present invention mixes with capacity polysiloxanes intermediate and prepares by containing the phenol component, and can be by many distinct methods preparations. A kind of method is that phenol is mixed with aldehyde and polysiloxanes intermediate. Another kind method is that the fusible bakelite that oneself is made by phenol and aldehyde reaction is mixed with formaldehyde donor and polysiloxanes intermediate. Also having a kind of method is that the resole resin that oneself is made by phenol and aldehyde reaction is mixed with the polysiloxanes intermediate. After solidifying, phenolic siloxane composition of the present invention has the better pliability of phenol resin composition and impact resistance than traditional not silicone-containing.
Phenolic siloxane composition of the present invention can be chosen wantonly and adopt following component preparation: (1) is reduced the reaction time relevant with generating the phenolic siloxane composition and is reduced the catalyst of reaction temperature; (2) improve liquidity the additive of pliability etc. and modifier; (3) use pigment and/or filler to obtain required color and/or denseness.
Phenolic siloxane composition constructed in accordance with the principles of the present invention comprises interpenetrating polymer networks (IPN). Various IPN of the present invention is comprised of chemically not identical cross-linked polymer chain; That is, siloxane polymer chain and novolac polymer chain do not have chemical bonds substantially between them. Siloxane polymer chain and novolac polymer chain are fixed together by nonvolatil chain entanglement. It will be appreciated that various IPN of the present invention does not comprise such composition, namely solid or solids are sandwiched in a kind of liquid phase or the polymerization phase, as solid silicon or siloxanes particle be sandwiched in novolac polymer mutually in.
The novolac polymer main chain that is IPN according to a key feature of the composition of principle of the invention preparation comprises siloxane group. When preparing in initial the synthesizing at phenolic siloxane, siloxane group is present in the uncured prepolymer, namely mix the uncured prepolymer that forms with aldehyde by phenol, and siloxane group also is present in cross-linked polymer, namely under any circumstance the novolac and resole resin. Siloxane group is present in the main chain of novolac polymer and not only as side group. These groups have improved the pliability of novolac polymer and have made the resistance to impact of the novolac polymer that comprises siloxanes and pliability be better than unmodified novolac polymer composition just, but do not sacrifice chemical proofing and heat resistance.
In the first embodiment, prepare the phenolic siloxane composition by mixing phenol or fortified phenol with aldehyde and polysiloxanes intermediate. Although phenol is preferred raw material, also can use various fortified phenols such as orthoresol, metacresol, paracresol, xylenols, nonyl phenol, styrene (styreated) phenol, bromophenol, catechol, p-t-butyl phenol, POP, nonylphenol, p-phenyl phenol, bisphenol-A, resorcinol, cashew nut shell liquid and composition thereof. Select which type of phenol or fortified phenol to depend on the source of goods of economic factor and this raw material as raw material, manufacturing process, or also depend on the desired properties of resulting composition.
As for aldehyde component, particularly preferably formaldehyde. Except formaldehyde, suitable aldehyde and the aldehyde donor that can be combined with phenol or fortified phenol with preparation phenolic siloxane composition comprises acetaldehyde, para-acetaldehyde, glyoxal, hexa, and furfural. The consumption of the aldehyde component of mixing with phenol determines to mix the type of the phenolic resins that generates, as generates fusible phenolic siloxane composition or solvable fusible phenolic siloxane composition. Need resole resin or novolac to depend on the property that the phenolic siloxane composition is required. When the aldehyde of phenol component and molar excess number and polysiloxanes intermediate mixed, reaction generated fusible phenolic siloxane composition. When the phenol component was mixed with the aldehyde of molal quantity in shortage, reaction generated solvable fusible phenolic siloxane composition.
For the polysiloxane intermediate, can use polysiloxane intermediate preparation alkoxy-functional and silanol-functional composition of the present invention.The polysiloxane intermediate of indication of the present invention is to have-polymkeric substance of Si-O-main chain and the chemical structure that can further react, and these reactions as hydrolysis and/or condensation are with generation cure polymer structure.A preferred class polysiloxane intermediate has following formula:
Each R wherein
2Be independently selected from hydroxyl, alkyl, aryl, aryloxy and have the alkoxyl group of 6 carbon atoms at the most, wherein each R
1Be independently selected from hydrogen, alkyl and at the most the aryl of 12 carbon atoms and n be 1 to 56 integer, it is between about 150 to about 10000 that its numerical value is elected the molecular-weight average that makes the polysiloxane intermediate as.The molecular weight that it is believed that selected polysiloxane intermediate may influence the novolac polymer that generated and siloxane polymer IPN the IPN degree and with the ratio of novolac polymer copolymerization with the siloxane groups that generates external phase.
Another group polysiloxane intermediate is the polysiloxane raw material of hydroxyl (OH) and comprises that those have the raw material of one or more hydroxyls that directly link to each other with Siliciumatom, as has the silanol raw material of following general formula
With
With
Each R wherein
5Can comprise being selected from alkyl alkenyl, cycloalkyl, aryl, the alkyl of alkaryl or aralkyl, and n
1It can be 1 to 30 integer.
Also have another group to contain the polysiloxane raw material of OH, this raw material comprises two or more OH groups that link to each other with Siliciumatom, and has two or more Siliciumatoms that connected by divalent organic group, those raw materials shown in following general formula:
Each R wherein
6Can comprise another OH base or comprise and be selected from alkyl, cycloalkyl, aryl, the alkyl of alkaryl and alkylaryl, R
7Can comprise and be selected from methylene radical, polymethylene, inferior aralkyl (aralyene), poly-inferior aralkyl, the divalent organic group of cycloalkylidene and poly-cycloalkylidene.
The polysiloxane intermediate that is used for methoxy functional of the present invention includes but is not limited to: DC-3074, DC-3037 (Michigan, the Dow CorningCorporation of Midland provides); SY-231 (molecular weight is about 1000) and MSE-100 (Wacker Silicone Corporation provides); And SR-191 (General Electric provides).The polysiloxane intermediate of silanol-functional contains the Si-OH of 0.5wt% to 6wt% that have an appointment usually.The polysiloxane intermediate of the commercially available silanol-functional that the present invention uses includes but is not limited to: diphenyl silanodiol (Diphenylsilandiol, molecular weight is about 216), Wacker Silicones SY-409 (molecular weight is about 10000) and SY-430; The following material that provides with DowCorning company: DC804, DC805, DC806A, DC840, Z-6018, DC-1-2530, DC-6-2230, DC-1-0409, DC-1-0410 and laminating resin 2103,2104 and 2106.
Preferred first embodiment for preparing solvable fusible phenolic siloxane composition is with phenol or fortified phenol, and aldehyde such as formaldehyde and a kind of polysiloxane intermediate mix.Be as the criterion with every moles of phenol feeding quantity, the amount of formaldehyde is between 0.75 to 0.90 mole, and the amount of polysiloxane intermediate is 0.01 to 0.3 mole.The mol ratio of typical phenol and formaldehyde is 1: 0.75～0.90 in novolac.Table 1 has provided the typical mole number scope of the different polysiloxane intermediate of the molecular weight that is used to prepare solvable fusible phenolic siloxane composition.
Table 1
| The polysiloxane intermediate | Molecular weight | 1mol phenol and 0.75mol formaldehyde | 1mol phenol and 0.90mol formaldehyde |
| Diphenyl silanodiol | ????216 | 0.01～0.3mol polysiloxane intermediate | 0.01～0.3mol polysiloxane intermediate |
| ????SY-231 | ????1000 | 0.01～0.2mol polysiloxane intermediate | 0.01～0.2mol polysiloxane intermediate |
| ????SY-409 | ????10000 | 0.01～0.05mol polysiloxane intermediate | 0.01～0.05mol polysiloxane intermediate |
Preferred first embodiment for preparing fusible phenolic siloxane composition is with phenol or fortified phenol, and aldehyde such as formaldehyde and polysiloxane intermediate mix.Be as the criterion with every moles of phenol feeding quantity, the amount of formaldehyde is 1 to 3mol, and the amount of polysiloxane intermediate is 0.01 to 0.7mol.The mol ratio of typical phenol and formaldehyde is 1: 1 to 1: 3 in the resol.Table 2 has provided the typical amounts scope of the polysiloxane intermediate with different molecular weight that is used to prepare fusible phenolic siloxane composition.
Table 2
| The polysiloxane intermediate | Molecular weight | 1mol phenol 1mol formaldehyde | 1mol phenol 3mol formaldehyde |
| Diphenyl silanodiol | ????216 | 0.01～0.7mol polysiloxane intermediate | 0.01～0.3mol polysiloxane intermediate |
| ????SY-231 | ????1000 | 0.01～0.02mol polysiloxane intermediate | 0.01～0.02mol polysiloxane intermediate |
| ????SY-409 | ????10000 | 0.01～0.05mol polysiloxane intermediate | 0.01～0.05mol polysiloxane intermediate |
For the solvable fusible phenolic siloxane composition of above-mentioned first embodiment and each in the fusible phenolic siloxane composition, need to use about 0.5 polysiloxane intermediate to the 35wt% scope.The phenolic siloxane composition that polysiloxane intermediate content is lower than first embodiment of about 0.5wt% has well heat-resisting, anti-combustion and chemical proofing, but with polysiloxane intermediate content is that 0.5 to 35wt% composition is compared, and snappiness reduces and fragility increases.Phenolic siloxane composition and the polysiloxane intermediate content that polysiloxane intermediate content is higher than first embodiment of about 35wt% is that 0.5 to 35wt% composition is compared the thermotolerance with reduction, flame resistivity and chemical proofing, but snappiness increases and has reduced fragility.
When the phenolic siloxane composition of preparation first embodiment, adopt catalyzer to generate needed novolac prepolymer or resol prepolymer.For example, when generating solvable fusible phenolic siloxane composition, use strong acid such as sulfuric acid, sulfonic acid, oxalic acid, or phosphoric acid is to promote the generation of novolac prepolymer.When generating fusible phenolic siloxane composition, use highly basic such as sodium hydroxide, calcium hydroxide or hydrated barta are to promote the generation of resol prepolymer.In preferred first embodiment, acid catalyst consumption about 5wt% at the most when preparing solvable fusible phenolic siloxane composition, and alkaline catalysts consumption about 5wt% at the most when preparing fusible phenolic siloxane composition.
Except that the catalyzer of the above, but when the phenolic siloxane composition of preparation first embodiment also arbitrariness use other catalyzer with by reducing the condensation that time relevant with this reaction and/or temperature promote resol and polysiloxane intermediate not essentially.But be used to promote the catalyzer of resol and the condensation reaction of polysiloxane intermediate and the phenolic siloxane composition that following arbitrariness is used to prepare the second and the 3rd embodiment not essentially, promptly those catalyzer by the feedstock production phenolic siloxane composition that comprises novolac and resol respectively are identical, and can same ratio use.
Earlier phenol and polysiloxane intermediate component are mixed when preparing the solvable fusible phenolic siloxane composition of first embodiment and fusible phenolic siloxane composition, add the aldehyde component then to form novolac polymer, siloxane polymer and phenolic aldehyde-siloxane polymer promptly have the IPN of the novolac polymer of Si-O group in the novolac polymer main chain.Before adding the aldehyde component, is a committed step with phenol and polysiloxane intermediate blended step in the composition of preparation first embodiment, reaches required degree because this step is guaranteed silanol in the polysiloxane intermediate and the reaction between the hydroxyl in the phenol component.As described below, the condensation reaction between the hydroxyl in silanol and the phenol component needs, because this reaction is introduced novolac polymer with the Si-O group, thereby improves the shock strength and the toughness of curing composition.Add after the aldehyde, silanol and newly-generated resol or novolac, be phenolic hydroxyl group and/or the methylol hydroxyl reaction in lower molecular weight resol or the novolac, further in resol, introduce the Si-O group so that aforesaid improved performance to be provided.
After each component is mixed, mixture temperature is improved the reaction times that generates the phenolic siloxane composition to reduce.
For example, can steamer formula blade or anchor stirrer be housed with one, the stainless steel reactor of the strap clamp cover of a steam condenser and a thermostat prepares the solvable fusible phenolic siloxane composition of first embodiment by batch technology.Typically, the phenol adding reactor with fusing starts agitator and adds the polysiloxane intermediate.After the polysiloxane intermediate, can add a kind of acid catalyst to promote the formation of solvable fusible novolac polymer.Then formalin (37～40% formalin) is added reactor, feeding in raw material, it is reinforced also can at high temperature to control before heating up.The result of violent condensation reaction is strong heat release.Condensation step is performed until and reaches the distribution of desired molecule amount, and mixture can become two-phase during this period, and resin-like components is separated.The real reaction time distributes according to the desired molecule amount, the use of one or more catalyzer, pH, and aldehyde: phenol: the mol ratio of polysiloxane intermediate and changing.
Each component is admixed together, phenol and polysiloxane intermediate react in a manner described during this period, phenol and aldehyde reaction generate fusible or novolac, and fusible or novolac and polysiloxane intermediate generation polycondensation, but this polycondensation arbitrariness is quickened by the effect of following catalyzer not essentially.During this period, the polysiloxane intermediate hydrolysis of any alkoxy-functional generates the polysiloxane intermediate of silanol-functional, but these two all homopolymerization generate siloxane polymer and can on its main chain, introduce the Si-O group with phenolic hydroxyl group copolymerization in phenol and the newly-generated novolac prepolymer.
Therefore, resulting composition comprises the IPN of solvable fusible novolac polymer and siloxane polymer and the external phase that is formed by the novolac polymer that has one or more siloxane groupss on the main chain.The hydrolysis of the polysiloxane intermediate of alkoxy-functional can arbitrariness be quickened by the effect of following catalyzer not essentially.Perhaps, can use the polysiloxane intermediate of silanol-functional in the method, this intermediate can be without hydrolysis directly and phenol and newly-generated novolac prepolymer.
Polycondensation phase can be passed through normal pressure after finishing, and decompression or vapor distillation remove and anhydrate residual moisture, unreacted phenol and lower-molecular-weight component.It is emphasized that distilation steps between the silanol of polysiloxane intermediate and phenolic hydroxyl group and resol hydroxyl, carry out condensation reaction after rather than before carry out because the silanol of significant quantity and phenol and newly-generated resol coexistence are necessary.Distillation end point is generally taken a sample by resin and is measured its melt viscosity and determine.After the resin cooling, available some kinds of modes are handled.Can bulk or sheet form sell, be deployed into the molding powder, or with hexamine (hexamine) and grinding of other filler and blending.
In another example, use the aforementioned device identical to prepare the fusible phenolic siloxane composition of first embodiment by batch technology with the solvable fusible phenolic siloxane composition for preparing first embodiment.Usually, fusion phenol is added reactor, start agitator and add the polysiloxane intermediate.Can add alkaline catalysts to promote the formation of fusible novolac polymer after adding the polysiloxane intermediate.Add formalin also with this batch materials heating.Just begun to be thermopositive reaction.Usually condensation is to carry out under the temperature of normal pressure and 60 to 100 ℃ or under refluxing.Because fusible phenolic siloxane composition itself is heat cured, dehydration is wanted to carry out to prevent overreact or gelling fast and at low temperature.Measure concrete hot plate gelation time and determine terminal point by manual, gelation time carries out and shortens with resinification.Fusible phenolic siloxane composition can be freezing to prolong its package stability.
The novolac of the second and the 3rd embodiment and resol silicone composition are that raw material prepares with novolac and resol respectively.The resol of any kind may be used to prepare phenolic siloxane composition of the present invention and the predetermined final application target of final basis is selected.Suitable resol can comprise based on phenol, fortified phenol such as p-cresol, and xylenol, dihydroxyphenyl propane, p-phenyl phenol, p-tert-butylphenol is to those of tert-octyl phenol and Resorcinol.Resol can by suitable phenol and aldehyde as the front in the first embodiment those aldehyde of introduction mix and prepare.Any mode of the basic building-up reactions of resol in can be in two ways carried out, and depends on that two kinds of principal reaction things are the ratio of phenol and aldehyde, also depend on the pH value of mixture.
As discussed above, the resol by the preparation of mixed phenol and aldehyde is included into a certain class, novolac or the resol in two classes usually.Novolac is thermoplastic material and prepares by heating phenol and formaldehyde (generally being formalin) in shortage in the presence of acid catalyst (normally oxalic acid or sulfuric acid).Crosslinked and gelation must take place otherwise understand less than 1 in the mole of formaldehyde/phenol (F/P) in preparation process.This reaction is strong heat release.The building-up reactions of novolac can be represented by the formula.
Novolac
This reaction at first generates various phenolic alcohol, carries out the condensation of phenolic alcohol again, and condensation reaction is carried out rapidly in excessive phenol, generates the novolac polymer than short chain, as comprises the polymkeric substance of 2 to 10 phenol rings, and wherein the phenol ring connects together by methylene radical.Novolac is a thermoplastic resin, contains the methylol functionality hardly, molecular weight ranges be about 125 to 5000 and glass transition temperature range be 45 ℃ to 100 ℃.Novolac self is further condensation not, unless add extra formaldehyde or other reactive feedstock, i.e. formaldehyde donor such as vulkacit H.Though most of cross-link bond is the methylene radical bridged bond in the novolac, confirmed also to exist the benzylamine structure.
Resol is a thermosetting resin, often is called single-order resol.Their preparation method is to use alkaline catalysts (caustic soda and the ammonia or the amine that are used for electrical grade laminating resin that normally are used for water soluble resin) heating phenol and formaldehyde (normally formalin).The mol ratio of formaldehyde and phenol (F/P) is greater than 1.The building-up reactions of resol can be represented by the formula.
Between the reaction period, phenol generation hydroxymethylation and condensation hardly.The gained phenolic alcohol can be condensed under these conditions and be created on the polymkeric substance that has ehter bond and methylene radical bridged bond between the phenol ring together.The more important thing is that the novolac polymer that this reaction generates also has many methylol side groups.According to the degree that the type of phenols raw material and reaction are carried out, resol can have structure very inequality and can be liquid or solid, and is water miscible or water-insoluble, alkalescence or neutral, slowly solidified or high reaction activity.The molecular weight ranges of typical resol is 150 to 2000.
But do not add any other solidifying agent self condensation when resol is heated and generate crosslinked novolac polymer.Yet,, can use acid catalyst to shorten set time if need.The suitable dispensable catalyzer of arbitrariness comprises mineral acid such as phosphoric acid, sulfuric acid or hydrochloric acid and organic acid such as tosic acid and phenylbenzimidazole sulfonic acid.Also can use the special inorganic acid and the organic acid that can discharge the active acid functionality when being heated.If need, can also use the curing resols such as magnesium oxide of dispensable alkaline catalysts of arbitrariness such as special use.
Can use any resol such as solvable fusible or resol to make the phenolic siloxane composition of the second and the 3rd embodiment in accordance with the principles of the present invention respectively.Concrete solvable fusible or being chosen in of resol depended on final purposes, needed physics of the finished product and chemical property, and using method that is adopted or complete processing to a great extent.
For example, twining legal system with long filament when making mixture such as glass fibre and strengthening structure,, can use low viscosity resol by phenol and prepared formaldehyde in order to reach best glass fibre wettability effect and final high content of glass fiber.Can use moderately viscous resol when making composition by molding methods.The resol that need use high sulfonic acid catalyzes agent content when making glass fibre reinforced composion by pultrusion is to guarantee very fast solidification rate.
For example, design as the chemical storage tank liner or jar and during the heat-curable coating of liner of tube, can be with the heat reactivity resol of phenol or substituted phenol.These resols are normal with Resins, epoxy and with so that chemical resistance and corrosion resistance nature reach the best.For example, the metal primer of self-vulcanizing can be in the short period of time before using be mixed and made into by resol and mineral acid (for example phosphoric acid, sulfuric acid or hydrochloric acid) or organic acid (tosic acid or phenylbenzimidazole sulfonic acid).
For example, the resol that is used to make moulding compound mainly is novolac, has wherein added 5% to 15% vulkacit H as the curing activity agent.These raw materials can powderies or are granularly mixed with glass fibre, mineral extender, rubber modifier etc., are used for making various products by compression molding, casting die, centrifugal modling method and injection moulding.
The most useful in the present invention solid dissolvable resol can be by the preparation of aforesaid any phenol and aldehyde, and molecular weight ranges is about 400 to 5000, and glass transition temperature range is about 40 ℃ to 90 ℃.The molecular weight ranges of the most useful resol is about 300 to 3000 in the present invention, solid content be 50wt% to 90wt%, and the content of free phenol or substituted phenol be 2wt% to 20wt%, and water-content is that 1wt% is to 10wt%.
The manufacturers of suitable resol comprises: B.P.Chemical Division of BritishPetroleum of Barry U.K.; The Packaging and Industrial ProductsDivision of Borden, Inc., of Columbus, Ohio; The Durez Division ofOccidental Petroleum of Dallas, Texas; Georgia-Pacific Corporation ofAtlanta, Georgia; Neste Resins Corporation of Eugene, Oregon, and many other small-scale manufacturerss.Some preferred resol comprise the Cellobond J2018L and the J2027L of B.P.Chemical company, the SL-898 resol of Borden company and the GP5018 resol of Georgia-Pacific company.
Comprise greater than the about novolac of 50wt% according to the phenolic siloxane composition of second embodiment of principle of the invention preparation, and preferably comprise the novolac of about 50wt% to the 95wt% scope.The phenolic siloxane composition of the 3rd embodiment comprises the resol greater than about 65wt%, and preferably comprises about 65wt% to 99.5wt%.
Novolac content is lower than about 50wt% in the phenolic siloxane composition, or resol content is when being lower than about 65wt%, formed composition is compared with the composition that each phenolic resin content is in preferable range, thermotolerance, and flame resistivity and chemical proofing descend.Novolac content is higher than about 95wt% in the composition, or resol content is when being higher than about 99.5wt%, formed composition is compared with the composition that each phenolic resin content is in preferable range, thermotolerance, flame resistivity and chemical proofing are good, but snappiness descends, and fragility increases.
For the polysiloxane intermediate, aforementioned those polysiloxane intermediates that are used to prepare the phenolic siloxane composition of first embodiment also can be used for preparing the phenolic siloxane composition of the second and the 3rd embodiment.Each can comprise the polysiloxane intermediate of 0.5wt% to the alkoxy-functional or the silanol-functional of 35wt% scope the phenolic siloxane composition of the second and the 3rd embodiment.
In second embodiment, solvable fusible phenolic siloxane composition is novolac to be mixed with formaldehyde donor and polysiloxane intermediate prepare.Suitable formaldehyde donor comprises formalin, polyoxymethylene ， trioxane, and vulkacit H etc., preferred raw material is a vulkacit H.The solvable fusible phenolic siloxane composition of second embodiment can comprise the formaldehyde donor of about 3wt% to the 15wt% scope.
When formaldehyde donor content is less than about 3wt% in the solvable fusible phenolic siloxane composition, that to be 3wt% compare degree of crosslinking to the composition of 15wt% scope is low and set time is longer for formed composition and formaldehyde donor content, thereby physicalies such as heat-resisting, anti-combustion and chemical proofing descend.When formaldehyde donor content is higher than about 15wt% in the solvable fusible phenolic siloxane composition, formed composition and formaldehyde donor content be 3wt% to the composition of 15wt% scope compare the degree of crosslinking height and also set time shorter, thereby this composition is difficult to processing and is used to make member and/or coating.
In the 3rd embodiment, fusible phenolic siloxane composition is to mix with the polysiloxane intermediate by resol to prepare.In case of necessity, can arbitrariness use acid or alkaline catalysts to reduce the resin needed reaction times of final curing not essentially.The suitable inorganic acid catalyst that arbitrariness is used not essentially in the 3rd embodiment comprises phosphoric acid, hydrochloric acid, and sulfuric acid.The suitable organic acid that arbitrariness is used not essentially in the 3rd embodiment comprises tosic acid and phenylbenzimidazole sulfonic acid.Suitable alkaline catalysts comprises various forms of barium oxide and magnesium oxide etc. to be used for the resol solidified.Commercially available special-purpose acid type catalyzer also can be used among the present invention, and the product of commodity Phencat 381 by name and Phencat 382 can be buied from British Petroleum Chemicals.Other special-purpose catalyst comprises Borden RC-901, the di(2-ethylhexyl)phosphate phenylester that a kind of Dover Corp. provides, GP3839 and the GP308D50 of its product Doverphos 231L by name and Georgia-Pacific.
The fusible phenolic siloxane composition of the 3rd embodiment can comprise at the most the approximately dispensable acid of 15wt% arbitrariness or alkaline catalysts or solidifying agent.Acid that comprises in the fusible phenolic siloxane composition or alkaline catalysts are during more than about 15wt%, resulting composition prepared composition when not being less than 15wt% with catalyzer or acid or alkaline catalysts consumption is compared, degree of crosslinking height and set time are shorter, thereby resulting composition is difficult to processing and is used to make member and/or coating.In case of necessity, second embodiment can arbitrariness comprises about at the most 15% any dispensable acid or alkaline catalysts with further minimizing set time not essentially.
In case of necessity, the first, the second when catalyzer that the phenolic siloxane composition of the 3rd embodiment separately can arbitrariness comprises capacity not essentially generates the phenolic siloxane composition to reduce with the condensation of polysiloxane intermediate and reaction times relevant thereof and reduce temperature of reaction with the copolymerization of novolac polymer.The use that is understood that this catalyzer is that arbitrariness is dispensable, and in principle preparation first according to the present invention, second, must not adopt during with the phenolic siloxane composition of the 3rd embodiment, because also can reach the purpose that reduces the reaction times by improving temperature of reaction without this catalyzer.
Suitable catalyzer is selected from organometallic compound, amine compound, and composition thereof.Preferred organometallic compound and amine compound and use when in the hydrolysis of catalysis polysiloxane intermediate and/or condensation, needing.Useful organometallic compound comprises known metal siccative of coating industry such as zinc, magnesium, cobalt, iron, the octylate of lead and tin, neodecanoate and naphthenate etc.Organic titanate such as butyl (tetra) titanate etc. also can be used for the present invention.
The preferred organometallic compound of a class as catalyzer is the organo-tin compound with following general formula
R wherein
8, R
9, R
10And R
11Be selected from the alkyl of 11 carbon atoms at the most, aryl, aryloxy, and alkoxyl group, and R
8, R
9, R
10And R
11In any two also optional self-contained halogens, the inorganic atoms of sulphur and oxygen.
Organo-tin compound as catalyzer comprises tin tetramethide, tetrabutyl tin, tetra octyl tin, tributyltin chloride, tributyl-methyl phosphonium vinylformic acid tin, dibutyl tin dichloride, Dibutyltin oxide, dibutyltin sulfide, di-n-butylacetic acid tin, dibutyl tin dilaurate, dibutyl toxilic acid tin polymkeric substance, dibutyl two bay tin mercaptides, stannous octoate, two (iso-octyl Thiovanic acid) tin of dibutyl, butyl tin trichloride, butyl stannonic acid (stannoic acid), dioctyl tindichloride, dioctyl tin oxide, dioctyl two lauric acid tin, dioctyl toxilic acid tin polymkeric substance, two (iso-octyl Thiovanic acid) tin of dioctyl, dioctyl tin sulfide and dibutyl 3-thiohydracrylic acid tin.
The phenolic siloxane composition of first, second and the 3rd embodiment can comprise at the most the approximately organo-metallic catalyst of 5wt%.When organometallic compound content is higher than about 5wt% in the phenolic siloxane composition, resulting composition is compared with the composition that is less than about 5wt% without catalyzer or organometallic compound content, has high degree of flexibility, because increased the hydrolysis and/or the condensation reaction of polysiloxane intermediate.In addition, do not use the phenolic siloxane composition of organo-metallic catalyst preparation to compare, need longer time and/or higher temperature just can reach desired condensation reaction degree with the phenolic siloxane composition that uses organometallic compound.
For amine compound, be used for the hydrolysis of not essential ground of arbitrariness catalysis polysiloxane intermediate and/or the preferred amines compound of condensation reaction and have following general formula
R wherein
12And R
13Respectively be selected from hydrogen, the aryl of 12 carbon atoms and alkyl at the most, and R
14Be selected from the alkyl of 12 carbon atoms, aryl and hydroxyalkyl at the most.
Suitable amine compound as catalyzer comprises dimethyl methyl hydramine, ethylaminoethyl alcohol, dimethylethanolamine, dimethyl propanol amine, dimethyl butyrate hydramine, dimethyl-penten hydramine, dimethyl hexanol amine, methylethyl carbinolamine, methyl propyl carbinol amine, the methylethyl thanomin, methylethyl Propanolamine, monoisopropanolamine, methyldiethanolamine, trolamine, diethanolamine, and thanomin.Preferred amine compound comprises dimethylethanolamine and ethylaminoethyl alcohol.
When needing, organometallic compound and amine compound can use separately with preparation phenolic siloxane composition.But, have found that when the two and time spent organometallic compound and amine compound in the catalytic curing process, can act synergistically, thereby more can reduce set time and/or temperature of reaction during than independent use organo-metallic or amine catalyst.So, in the situation that needs use, preferably with organometallic compound and amine compound and usefulness, so as not only can be in the situation of the polysiloxane intermediate that uses alkoxy-functional the hydrolysis of catalysis polysiloxane intermediate generate hydroxyl (hydroxide) reaction but also can the catalysis alkoxyl group and the condensation polymerization of the polysiloxane intermediate of silanol-functional.An example of organo-metallic and amine compound and usefulness is dibutyl tin acetate and ethylaminoethyl alcohol.Concerted reaction was with the catalytic curing process when dibutyl tin acetate and this amine were used with.Have mechanical characteristics although it is believed that the synergistic effect of this organo-tin compound and this amine compound, exact mechanism it be unclear that.
And with organometallic compound and amine compound with a unanticipated of preparation phenolic siloxane composition of the present invention to effect be to have improved processibility.With the fusible phenolic siloxane/latent acid catalyst type composition of organo-metallic and amine catalyst preparation with compare without the catalytic composition of organo-metallic/amine, increase working life and set time constant substantially or shortened.In fact, increase set time that latent acid catalyst content makes phenol resin composition during above-mentioned composition and simple resol/the latent acid catalyst system is suitable in preparation, but obviously prolong working life.The accident of resulting composition processibility is improved really the cutter reason and be it be unclear that, but can believe that this is relevant to the neutralization of latent acid catalyst with amine compound.
The phenolic siloxane composition of first, second and the 3rd embodiment can comprise the amine catalyst of about 5wt% at the most.When amine compound content is higher than about 5wt% in the phenolic siloxane composition, formed composition is compared with the composition that is not less than 5wt% preparation with amine compound or amine compound consumption has higher snappiness, and this is because the hydrolysis of polysiloxane intermediate and/or condensation reaction strengthen.In addition, the phenolic siloxane composition that prepares with amine catalyst is not compared with the phenolic siloxane composition that uses the amine catalyst preparation and is reached longer time of required condensation reaction degree needs and/or higher temperature.
The preferred proportion of the two is approximately 1 to 1 when organic metallic compound is used as catalyzer with amine compound.Therefore, first, second can comprise at the most approximately mixing organo-metallic and the amine catalyst of 10wt% with the 3rd phenolic aldehyde silicone composition.Therefore, can comprise at the most the approximately catalyzer of 25wt% by the phenolic siloxane composition that mixes the preparation of organo-metallic and amine catalyst and the dispensable acid of arbitrariness or alkaline catalysts.The range of catalysts that preferred first, second and the 3rd phenolic aldehyde silicone composition comprise can reach the 5wt% of whole compositions to 25wt%.
Water can moisture resol form or exist with the form of formalin.For example, resol can comprise the water of 3wt% to the 12wt% scope, and formaldehyde can comprise formalin, and it is the formalin of about 37-40%.When using the polysiloxane intermediate preparation composition of alkoxy-functional, need water to promote the alkoxyl group hydrolysis.These water may reside in the phenolic aldehyde composition or in the course of processing and absorb from air.But, should be understood that the phenolic siloxane composition according to principle of the invention preparation can not add water or prepare under the situation without any solvent.Non-water resol or novolac, promptly not containing the resol that adds water can rather than use in the situation of polysiloxane intermediate preparation composition of alkoxy-functional and use at the polysiloxane intermediate that uses silanol-functional, because do not need the hydrolysis of polysiloxane intermediate this moment.
It is very low or be zero resol that the phenolic siloxane composition of first, second and the 3rd embodiment can be made water content, and it has better fire performance and processibility.The polysiloxane intermediate is being produced when having low viscous stable product usually as a kind of reactive diluent.
The phenolic siloxane composition of the second and the 3rd embodiment can allow solvable fusible or resol mix according to the above ratio with the polysiloxane intermediate of a kind of methoxyl group or silanol-functional to prepare.Keep this resol contact with the polysiloxane intermediate required time as 1 hour to carry out the condensation reaction of enough degree between the silanol of guaranteeing the polysiloxane intermediate and the phenolic hydroxyl group, thereby introduce the Si-O group of aequum in resol, promptly siloxanes replaces.This will finish before the resol copolymerization.
In second embodiment, add formaldehyde donor.But the words that need also arbitrariness add the catalyzer of resol and the catalyzer of polysiloxane intermediate not essentially, and promptly organometallic compound and/or amine compound are to shorten reaction and set time and to reduce temperature of reaction.
Each component is mixed until reaching even, resol carries out polycondensation to form novolac polymer during this period, this polycondensation is promoted by formaldehyde donor in second embodiment, but and in the 3rd embodiment this polycondensation arbitrariness be that acid or alkali effect are quickened by catalyzer not essentially.During this period, the polysiloxane intermediate of alkoxy-functional is proceeded hydrolysis, generates the polysiloxane intermediate of silanol-functional.Polymerization had both taken place and had generated siloxane polymer in the polysiloxane intermediate of silanol-functional, and promptly the siloxane polymer chain of IPN carries out condensation further to introduce the Si-O group in novolac polymer with novolac polymer again.
But the hydrolysis arbitrariness of the polysiloxane intermediate of alkoxy-functional is quickened by the katalysis of organometallic compound and amine compound not essentially.Therefore, resulting composition comprises the IPN of novolac polymer and siloxane polymer, and wherein the main chain of novolac polymer has siloxane groups.According to the difference of selected concrete batching and ratio thereof, be 1 to 3 hour the working life of Zhi Bei phenolic siloxane composition by this way.
In addition, the phenolic siloxane composition can be made three compositions system (not adding water) in accordance with the principles of the present invention, its preparation method is by suitable proportion polysiloxane intermediate and the dispensable organometallic compound of any arbitrariness and amine compound to be mixed in first container, and this material can be stored to before the use always.In second container, store resol, and the dispensable resol catalyzer of the formaldehyde donor in second embodiment and any arbitrariness respectively is stored in the 3rd independent container, and they mixed the formation composition with the polysiloxane intermediate mixture in first container before using.For example, can each component in each container be mixed with a metering mixed allocation machine when making glass filament phenolic aldehyde pipe, and mixed raw materials injected or pump into the pressurize jar, glass filament passes through this jar.
Can do not believed that by any concrete theory or mechanism constraint phenolic siloxane composition of the present invention generates in the following manner although do not wish.Use phenol, when aldehyde and polysiloxane intermediate are the phenolic siloxane composition of initial batching preparation first embodiment, (see P.w.Kopp according to well-verified principle, resol, polymer science and engineering encyclopedia, Vol.11, second edition, 45-95 page or leaf (1988), this book is hereby incorporated by reference document) infer and not only can generate resol but also can generate novolac.
When the product of preparation first embodiment, silanol in the polysiloxane intermediate and phenolic hydroxyl group reaction when two kinds of batch mixes according to inferring, thus in the phenol component, introduce the Si-O group.After in this mixture, adding the aldehyde component, silanol continuation and phenolic hydroxyl group and/or newly-generated be the phenol methylol hydroxyl reaction of low-molecular-weight resol.Since during the resol homopolymerization, there is silanol, their continuation and phenolic hydroxyl group and/or methylol hydroxyl reaction, and then continue in resol, to introduce the Si-O group.Silanol in the polysiloxane intermediate is also reacted with the silanol of other polysiloxane intermediate, generates siloxane polymer.
It is believed that the similar following reaction mechanism that 1-6 discussed of mechanism that these reactions take place.But should be understood that in the novolac polymer of first embodiment introducing siloxanes may follow reaction mechanism outside the mechanism of special introduction and explanation.In addition, all the other these reaction mechanisms may produce and those special different phenolic siloxane structures of mechanism of introducing and illustrating according to inferring.
In the fusible phenolic siloxane composition that forms the 3rd embodiment, when using dispensable acid of a kind of arbitrariness or alkaline catalysts to solidify resol, resol and other resol carry out polymerization and generate the solidified resol shown in the following reaction 1.
Reaction #1
When generating the solvable fusible phenolic siloxane composition of second embodiment, novolac and other novolac and formaldehyde, or formaldehyde donor carries out polymerization and generates the solidified novolac shown in the following reaction 2.Can think that the bridged bond between the most of phenolic group group is a methylene radical, but also have the benzylamine structure.
Reaction #2
But it is also not fully aware of that formaldehyde adds to the polymeric exact mechanism that reaches subsequently on the phenolic group of novolac.
If mix to prepare the composition of the second and the 3rd embodiment respectively with the polysiloxane intermediate of alkoxy-functional and novolac or resol and the dispensable organo-metallic/amine catalyst of arbitrariness, can think that the polysiloxane intermediate at first is hydrolyzed to generate the polysiloxane intermediate and the alcohol of silanol-functional by the mode shown in the following reaction 3.
Reaction #3
No matter the polysiloxane intermediate or the silanol of the polysiloxane intermediate of silanol-functional that are the alkoxy-functional of hydrolysis all can be reacted by the different mechanism of many kinds with the phenolic aldehyde prepolymer.A kind of mechanism is arranged shown in following reaction 4, the phenolic hydroxyl group in silanol and the solidified resol carries out condensation reaction the Si-O group is introduced novolac polymer.
Reaction #4
Silanol in the polysiloxane intermediate of silanol-functional also can be introduced novolac polymer with the Si-O group by mode shown in the following reaction 5 and phenol methylol hydroxyl reaction.
Reaction #5
Polysiloxane intermediate and resol prepolymer are considered to the shock-resistance of phenolic siloxane composition, the major cause of tensile strength and modulus in flexure improved performance by reaction 4 and 5 condensation reactions of carrying out.
The silanol of polysiloxane intermediate also can be carried out condensation reaction with the silanol of other polysiloxane intermediate and be generated siloxane prepolymer.This siloxane prepolymer can carry out condensation reaction with the phenolic aldehyde prepolymer by preamble is described, or generates the crosslinked polysiloxane network by carrying out polycondensation with siloxane prepolymer shown in the following formula reaction 6.Reaction #6
Therefore, phenolic siloxane composition of the present invention comprises by siloxane polymer, the IPN that novolac polymer is formed, and wherein the novolac polymer main chain has the Si-O group.Siloxane polymer in the composition also can be crosslinked with other siloxane polymer.In addition, to a certain degree crosslinked can also take place between the novolac polymer and/or between phenolic aldehyde and the siloxane polymer.
Can think phenolic siloxane composition shock strength and flexible improvement be because: there is linear siloxane polymer in (1), forms the IPN of siloxane polymer and novolac polymer; (2) in novolac polymer, there is silicone copolymers; (3) there is the siloxane polymer of cross-linked form.
To better understanding be arranged to the characteristic and the advantage of the phenolic siloxane composition of principle according to the present invention preparation with reference to following examples.
Table 3 has been listed the component that is used to make 2 inches (50mm) internal diameter glass reinforced pipes, and these pipes adopt traditional filament winding process to be made by the fusible phenolic siloxane composition (embodiment 2 and 3) of unmodified resol (embodiment 1) and the 3rd embodiment.Table 4 has gathered the The performance test results of embodiment 1,2 and 3 pairing various pipes in the table 3.
Table 3
Embodiment 1
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | |||
| ?PBW | ??1％ | PBW | ??1％ | PBW | ??1％ | |
| Cellobond J2027L (resol) | ??100 | ??91 | ??85 | ??70 | ??85 | ??70 |
| Phencat 381 (resol catalyzer) | ??10 | ???9 | ??14 | ??11 | ??14 | ??11 |
| DC-3074 (polysiloxane intermediate) | ??- | ??- | ??15 | ??12 | ??- | ??- |
| The DC-3074 of hydrolysis (polysiloxane intermediate) | ??- | ??- | ??- | ??- | ??15 | ??12 |
| Dibutyl tin acetate (catalyzer) | ??- | ??- | ??4 | ??3 | ??4 | ??3 |
| Ethylaminoethyl alcohol (catalyzer) | ??- | ??- | ??4 | ??3 | ??4 | ??3 |
| Working life (hour) | ?????????1.5 | ?????????2.5 | ?????????2.5 | |||
| Solidify the performance of pipe | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Proportion | ????1.85 | ????1.95 | ????1.96 |
| Content of glass fiber (wt.%) | ????73.1 | ????74.0 | ????72.2 |
| External diameter (inch) | ????2.709 | ????2.418 | ????2.408 |
| Thickness (inch) | ????0.159 | ????0.164 | ????0.159 |
| Short-term burstpressures (psi) | ????3,500 | ????4,100 | ????4,200 |
| Hoop stress (psi) | ????25,000 | ????28,180 | ????29,700 |
| Shock strength (2 pounds of steel balls) | ????24” | ????48” | ????60” |
| Combustion experiment | By | By | By |
With BP Cellobond J2027L (resol) and the unmodified resol pipe of Phencat381 (latent acid catalyst) mixing manufacture.Embodiment 2
Fusible phenolic siloxane composition by third embodiment of the invention is made the resol pipe, said composition adopts resol and the latent acid catalyst identical with embodiment 1, and add 15wt%DC-3074 (molecular-weight average that Dow Corning provides be 1400 and methoxy content be the polysiloxane intermediate of the methoxy functional of 15-25%), 4wt% dibutyl tin acetate (organo-metallic catalyst that is used for the polysiloxane intermediate) and 4wt% ethylaminoethyl alcohol (amine catalyst that is used for the polysiloxane intermediate).With traditional method with each component formation uniform mixture admixed together.Embodiment 3
Make the resol pipe by the mode identical with embodiment 2, different be that DC-3074 with hydrolysis in advance replaces the not DC-3074 of hydrolysis in advance.The preparation of the DC-3074 of hydrolysis in advance is with 3640g DC-3074, the 153.4g deionized water, and 153.4g methyl alcohol, 220g dimethylbenzene and 16.25g glacial acetic acid are added to one heating jacket are housed, in the 5000ml round-bottomed flask of agitator and condenser.Heated mixt makes it to reflux and kept about 2 hours.On flask, adorn a still head and receptor then, collect distillate and reach 300 °F (150 ℃) until room temperature.The product that obtains is the DC-3074 of thickness, slightly muddy liquid state hydrolysis in advance.
Prepare each phenolic siloxane composition of about 4000g and sneak into one 1 gallon the jar in, be transferred to again in the pressurize jar.Fibre glass roving is by the phenolic siloxane composition and be wound on the reciprocating type tubing machine on hollow steel volume core to reach desired thickness.Then by steam/water mixture is solidified each pipe about 30 minutes down at 140-190 °F (60-88 ℃) by blank coil core in being somebody's turn to do.Afterwards take off this pipe and descended after fixing about 2 hours again at 250 °F (120 ℃) from the volume core.
Embodiment 2 and 3 composition, i.e. the fusible phenolic siloxane composition that makes according to third embodiment of the invention, each all has about 2.5 hours working life, and be 1.5 hours the working life of the unmodified phenol resin composition of embodiment 1.The glass reinforced pipe of being made by the phenolic siloxane composition of embodiment 2 and 3 also demonstrates short-term burstpressures, hoop stress and the shock strength more much higher than the glass reinforced pipe made from the unmodified resol of embodiment 1.
Particularly, when phenolic siloxane composition tubulation of the present invention is used in the pipe explanation that makes by embodiment 2 and 3, compare with traditional resol pipe of embodiment 1, shock strength significantly increases.Relatively these embodiment can find that the shock strength of the pipe of embodiment 2 and 3 is more than two times of pipe of embodiment 1, and this demonstrates the benefit of using capacity polysiloxane intermediate preparation phenolic aldehyde composition to be brought according to the principle of the invention.
In addition, embodiment 2 and 3 phenolic siloxane composition also have than the higher proportion of embodiment 1 composition, show that formed composition has the foaminess of reduction and the microporosity of reduction.Produce this effect really cutter reason it be unclear that.But, can think that the polysiloxane intermediate just reacts with portion water before the water volatilization in solidification process in resol, reduce and carried the water yield secretly, generate thereby reduce micropore.The minimizing of micropore growing amount makes the solidified resol have higher tensile strength and modulus in flexure, and then improves impact property.
The minimizing of micropore growing amount also makes the solidifying product of made have lower water-absorbent.Can think that the existence of siloxanes also can make cured compositions hydrophobic in the phenolic siloxane composition except improving shock strength and snappiness.Phenolic aldehyde composition with water-intake rate of the microporosity of reduction and relevant therewith reduction can satisfy the requirement of making the product that is used for the electric insulation occasion that needs contact with water.An example of this application is to be used for electric train the 3rd guide rail coating composition made according to Mil Spec M14G.
Not finding has detrimentally affect to the resistivity against fire of phenolic siloxane pipe.All three individual system have all been passed through the test of 5 minutes 1000 ℃ of jet flamess and unburn.Therefore, phenolic siloxane composition of the present invention has above-mentioned advantage and improvement and does not damage the anti-combustion of resol inherent, heat-resisting and chemical proofing.These embodiment clearly show the advantage and the improvement of being given by phenolic siloxane composition of the present invention.
Table 5 has been concluded the result of the chemical-resistant resistance property testing of the casting spare of making by unmodified resol with according to the fusible phenolic siloxane composition of the 3rd embodiment of principle of the present invention preparation.
Table 5
Embodiment 4-6
| Weight (g) | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Cellobond J2027L (resol) | ????150 | ????150 | ????150 |
| DC-3074 (polysiloxane intermediate) | ????0 | ????15 | ????30 |
| Phencat 381 (resol catalyzer) | ????12 | ????21 | ????21 |
| Dibutyl tin acetate (catalyzer) | ????0 | ????1.4 | ????1.4 |
| Ethylaminoethyl alcohol (catalyzer) | ????0 | ????1.2 | ????1.8 |
| 37％HCl(180°F) | ???6.6521g | ???5.6433g | ???5.5134g |
| Dry weight | ???6.3483g | ???5.5378g | ???5.5728g |
| Weight increase/loss | ??-4.567％ | ??-1.869％ | ??+1.077 |
| 50％NaOH(180°F) | ???5.5000g | ???6.2269g | ???6.5439g |
| Dry weight | ???5.2278g | ???6.3208g | ???7.0039g |
| Weight increase/loss | ??-4.949％ | ??+1.508％ | ??+7.029％ |
| 30％HNO 3(80°F) | ???5.7074g | ???6.676g | ???6.0638g |
| Dry weight | ???1.286g | Dissolving | Dissolving |
| Weight increase/loss | -0.77467849 | ||
| 50％H 2SO 4(180°F) | ???6.292g | ???5.9112g | ???5.6498g |
| Dry weight | ???6.0008g | ???5.6563g | ???5.5082g |
| Weight increase/loss | ??-4.628％ | ??-4.312％ | ??-2.506％ |
| Ethanol (140) | ???5.6487g | ???6.475g | ???5.3084g |
| Dry weight | ???6.4175g | ???5.4117g | ???5.5435g |
| Weight increase/loss | ??+13.610％ | ??-16.422％ | ??+4.429％ |
| 50% acetate (180) | ????5.5196g | ????5.8308g | ????4.8967g |
| Dry weight | ????5.2912g | ????5.8939g | ????4.9778g |
| Weight increase/loss | ???+2.55％ | ???+1.68％ | ???+1.66％ |
| Distillation H 2O(180°F) | ????5.3084 | ????6.0035 | ????5.5134 |
| Dry weight | ????5.2869 | ????6.0021 | ????5.4446 |
| Weight increase/loss | ???-0.41 | ???-0.02 | ???-1.25％ |
In embodiment 4, make casting spare with the composition that comprises traditional unmodified resol.Embodiment 5 and 6 is casting spares of using the chemical ingredients identical with previous embodiment 2 and 3 to make by the phenolic siloxane composition of third embodiment of the invention.Each prescription all is at room temperature to mix in a plastic beaker, pours 12 then into " * 1 " (in 30 * 2.5cm) punching blocks to the height of about 5/16 inch (8mm).Casting spare solidified 1 hour at 150 °F (65 ℃), solidified 5 hours at 250 °F (120 ℃) then.Each casting spare is cut into 2 inches (5cm) length and solidified 1 month under 70 (21 ℃) and 50% relative humidity then.Per 2 inches long casting spares of weighing on analytical balance also immerse in the chemical reagent of test.After soaking for two weeks, sample taken out, cleans and in 250 °F (120 ℃) dry 1 hour, and then weigh to fixed temperature.
Surprisingly, embodiment 4,5 and 6 test-results show that the casting spare made from the fusible phenolic siloxane composition of the 3rd embodiment compares with the unmodified casting spare made from resol separately, and the tolerance of chemical substances such as organic and mineral acid, alkali and alcohol is improved.
Phenolic siloxane composition exhibiting according to principle of the invention preparation goes out the physicalies such as snappiness, shock-resistance and modulus in flexure of improvement, but does not influence physicalies such as resol inherent thermotolerance, flame resistivity and chemical proofing.In addition, phenolic siloxane composition according to principle of the invention preparation has reduced the formation amount of micropore and therefore itself and traditional phenol resin composition that does not contain siloxanes has been compared on density more near theoretical density, this may be because the water reaction in polysiloxane intermediate and the resol is carried secretly due to the water yield thereby reduced.
Phenolic siloxane composition according to principle of the invention preparation is compared with the phenol resin composition that does not contain siloxanes, has also improved the coating character to matrix (or as the bottom matrix time).Can think that the improvement of coating character is that silanol provides the bounding force of strengthening when said composition is used as the coating that imposes on certain matrix or is used as the support coating of material owing to have silanol in the composition.Phenolic siloxane composition of the present invention can the mode identical with traditional resol be used to make member, and as casting spare, coating is as coating on the glass reinforced pipe etc.Embodiment 7
The fusible phenolic siloxane composition for preparing first embodiment by the following method: the phenol adding of about 385g fusing is equipped with in the 1000ml flask with three necks,round bottom of heating jacket.This flask is heated to about 125 °F (52 ℃) and adds about 60.4g SY-231 (polysiloxane intermediate) and 7.7g 50% sodium hydroxide when stirring.The blended material was kept about 60 minutes under the temperature of about 120 to 130 (49 ℃ to 54 ℃) scopes.Add about 370g 50% formaldehyde in this mixture and in about 20 minutes, make temperature be raised to 190 °F (52 ℃ to 87 ℃) from about 126 °F, kept about 20 minutes.Attemperation and under the temperature of 185 to 195 (85 ℃ to 90 ℃) scopes, keeping about 90 minutes then.Mixture is decompressed to about 15mmHg vacuum, and temperature remains on 140 to 200 (60 ℃ to 93 ℃) scopes, steams and collect fraction 40 minutes.
The Brookfield viscosity of the fusible phenolic siloxane composition that makes by this way when 77 (25 ℃) is approximately 28000 centipoises, water-content be 2wt% to 3wt%, the weight-average molecular weight that gel permeation chromatography (GPC) is measured is less than about 580.Embodiment 8
The solvable fusible phenolic siloxane composition for preparing first embodiment by the following method: one of the phenol adding of about 517g fusing is equipped with in the 1000ml flask with three necks,round bottom of heating jacket.In the phenol of fusing, add about 619 SY-231 (polysiloxane intermediate) and about about 150 °F (65 ℃), stirred 1 hour.In mixture, add about 15g oxalic acid and stirred 5 minutes.In mixture, add molten oxymethylene (50% solution) and in 20 minutes, flask is heated to about 205 °F (96 ℃).Mixture kept 5 hours at about 205 °F (96 ℃).Mixture is decompressed to about 10mmHg.Distillation was also collected fraction about 2 hours, made temperature be raised to about 350 °F (176 ℃).Flask is cooled to about 230 °F (110 ℃), discharges vacuum at this moment and product is moved in the suitable container.
The solvable fusible phenolic siloxane composition that makes by this way at 266 °F (130 ℃) (at 12000S
-1Down, rotation 4105) ICI melt viscosity is about 3 pools, and the weight-average molecular weight that GPC measures is about 3102, and number-average molecular weight is about 1543.
Phenolic siloxane composition by principle of the invention preparation can the mode identical with traditional resol use, except having inherent flame resistivity, thermotolerance, chemical proofing, wear resistance, also provide the shock strength of improving, toughness, scratch by modulus rebound resilience.
For example, phenolic siloxane composition of the present invention can be used to make matrix material.Matrix material is meant heterogeneous system or comprises matrix material and the structure of strongthener, combination results unexistent structural performance of some any one-component or functional performance.The phenolic siloxane composition can partly or entirely be used as tackiness agent in this matrix material, and strongthener can be a fiber, particle, and metal strip, timber etc., they and tackiness agent are bonding, or are bonded together by tackiness agent.
Phenolic siloxane composition of the present invention can be used for making the fibre reinforced plastics of various matrix materials such as forms such as mo(u)lded item, section bar, is used for automobile, mass transport, building structure, aviation and national defence, and mining industry and tunneling industry are to improve snappiness, shock-resistance and toughness.The object lesson of these matrix materials is pipes with fortifying fibre or long filament 10 as shown in Figure 1.These pipes can resemble embodiment 1-3 and twine and bonding and make with phenolic siloxane composition of the present invention through long filament described, these long filaments are by glass fibre, Kevlar (aromatic polyamide) fiber, carbon fiber, graphite fibre etc. or their mixture are made.Described as above embodiment 1-3, the long filament winding tube that uses phenolic siloxane composition of the present invention to make has the hoop stress and the shock-resistance of improvement than the pipe made from unmodified resol.
The phenolic siloxane composition also can be used for making long filament enhanced steel pipe 12, as shown in Figure 2, this pipe by steel wire winding and long filament winding in conjunction with and bonding and make by phenolic siloxane composition of the present invention.
As other example, phenolic siloxane composition of the present invention can be used as tackiness agent and is used for building panel, as be used to make wood composite board 14 as glued board, shaving board, and the glued board (strand board) (as shown in Figure 3) of thin plate (waferboard)/orientation, so that improve snappiness and moisture resistance.
As other example, phenolic siloxane composition of the present invention can be used to make as shown in Figure 4 foam 16 to improve rebound resilience and water tolerance.This foam can be made by following four kinds of components: (1) phenolic siloxane composition; (2) whipping agent; (3) abscess control agent/tensio-active agent; (4) acid hardening agent/catalyzer.Being everlasting adds tensio-active agent in the resin, thereby number of components to be mixed reduces to 3 will foam the time.From chemically, foaming process depends on the thermopositive reaction between phenolic siloxane composition and the acid hardening agent.The heat of releasing makes volatile foaming agent (as freonll-11 or pentane) boiling, and whipping agent is dispersed in the phenolic siloxane composition with the small droplets form in advance.The phenolic siloxane composition just is blown to foam like this, and when uphill process was finished, composition was solidified into the inflexible thermosetting material.This foam is used for also needing fire-retardant insulation simultaneously, as goods transport vehicle, and business aircraft etc.The foam of being made by the phenolic siloxane composition has better rebound resilience and snappiness, does not have damaged the installation thereby help foamy.
As another example, phenolic siloxane composition of the present invention can be as the tackiness agent of making the friction materials mixture, as be used for the brake belt material 18 (shown in Fig. 5 a) of the brake shoes of automobile etc. and pad and be used for the clutch lining 20 (shown in Fig. 5 b) of the clutch plate of automobile etc.In this Application Areas, the use of phenolic siloxane composition has improved toughness and shock-resistance.
As another example, phenolic siloxane composition of the present invention can with natural rubber and many kinds of synthetic rubber and usefulness, be applied to cement, tackiness agent, travelling belt, flexible pipe and footgear etc. as rubber stiffener.The use of phenolic siloxane composition has improved the snappiness and the toughness of this type of material, and has reduced moisture content.
As another example, phenolic siloxane composition of the present invention can be separately or with other material blending after be used to make wash primer, industrial coating, paint and/or varnish, compare the moisture content that these products have better coating character, snappiness, shock strength, toughness and reduce with traditional resol that does not contain siloxanes.
As another example, phenolic siloxane composition of the present invention can be used as the tackiness agent in the production of felt insulating material, as the liner of upholstery, the mattress material is used for the cushion material and the automobile liner of wrapping material, thermal insulating material is as glass and mineral fibre.In these Application Areass, use the phenolic siloxane composition can improve snappiness, thereby help the installation of these insulating material, needn't worry to tear or the considerable change of flame retardant resistance.
As another example, phenolic siloxane composition of the present invention can be used for making the tackiness agent of bonding material, emery wheel 22 as shown in Figure 6, cutting wheel etc., and coated abrasives such as sand paper, emery cloth and emery wheel.In these Application Areass, use the phenolic siloxane composition can improve performances such as shock-resistance and toughness.
As another example, phenolic siloxane composition of the present invention can be used as the tackiness agent of high quality silica sand in the core rod of making the many metals of cast and mould.In this Application Areas, use the phenolic siloxane composition can make core rod and mould that better toughness is arranged, snappiness, shock-resistance and have the moisture content of reduction.
For example, that phenolic siloxane composition of the present invention can be used for making is electric, machinery and decorative laminate, and these veneer sheets comprise the substrate that multilayer applies to together phenolic siloxane composition by heat pressure adhesive.In this Application Areas, use the phenolic siloxane composition can improve physicalies such as shock-resistance, snappiness and toughness, and reduce moisture content.Although introduce the limited embodiment of phenolic siloxane composition at this, many improvement and variation are simple and clear concerning those those skilled in the art that.Therefore, should be clear, the phenolic siloxane composition can prepare with the mode beyond the concrete grammar described here in accordance with the principles of the present invention within the scope of the appended claims.
Claims (49)
1. phenolic siloxane composition comprises the interpenetrating polymer networks of novolac polymer and siloxane polymer.
2. the described phenolic siloxane composition of claim 1 comprises the Si-O group in novolac polymer.
3. the described phenolic siloxane composition of claim 2, the wherein not siliceous solids of said composition.
4. phenolic siloxane composition, by mixing following component preparation:
A kind of phenol that is selected from, ortho-cresol, meta-cresol, p-cresol, nonyl phenol, styrenated phenol, bromophenol, pyrocatechol, p-tert-butylphenol, to octyl phenol, to nonyl phenol, p-phenyl phenol, dihydroxyphenyl propane, Resorcinol, and composition thereof phenolic compound;
A kind of aldehyde;
A kind of acid or alkali; With
A kind of polysiloxane intermediate;
Wherein said composition comprises the interpenetrating polymer networks of novolac polymer and siloxane polymer.
5. the described phenolic siloxane composition of claim 4, wherein novolac polymer has the Si-O group in its main chain.
6. the described phenolic siloxane composition of claim 4, every mol phenol comprise 1 to 3mol aldehyde and 0.01 to 0.7mol polysiloxane intermediate.
7. the described phenolic siloxane composition of claim 4, the catalyzer that comprises capacity is being lower than under about 100 ℃ temperature processing and is solidifying to promote said composition.
8. the described phenolic siloxane composition of claim 7, wherein catalyzer is selected from organometallic compound, amine compound, acid, alkali, and composition thereof.
9. mixture with resin Composition, this resin Composition comprise the phenolic siloxane composition according to claim 4 preparation.
10. a phenolic siloxane composition, preparation by the following method:
Phenol and polysiloxane intermediate are mixed the formation mixture, and in this mixture, add:
A kind of aldehyde;
A kind of acid or alkali;
A kind of polysiloxane intermediate; With
A kind of organometallic compound that is selected from, amine compound, acid, alkali, and composition thereof catalyzer;
Wherein said composition comprise the interpenetrating polymer networks of siloxane polymer and novolac polymer and wherein novolac polymer on its main chain, have the Si-O group.
11. the described composition of claim 10, wherein catalyzer be the mixture of a kind of organometallic compound and a kind of amine compound and wherein organometallic compound be a kind of organo-tin compound with following general formula
R wherein
8, R
9, R
10And R
11Respectively be selected from alkyl, aryl, the aryloxy of 11 carbon atoms at the most, and alkoxyl group, and R
8, R
9, R
10And R
11In any two also optional self-contained halogens, the inorganic atoms of sulphur and oxygen.
12. the described composition of claim 11, wherein amine compound has following general formula
R wherein
12And R
13Respectively be selected from hydrogen, the aryl and the alkyl of 12 carbon atoms at the most, and R
14Be selected from the alkyl of 12 carbon atoms, aryl and hydroxyalkyl at the most.
13. the mixture with resin Composition, this resin Composition comprise the composition according to claim 10 preparation.
14. a phenolic siloxane composition, by mixing following component preparation:
A kind of resol;
A kind of polysiloxane intermediate; With
A kind of catalyzer that promotes the interpenetrating polymer networks formation of novolac polymer and siloxane polymer, wherein novolac polymer comprises the Si-O group on its main chain.
15. the described composition of claim 14 comprises the resol that accounts for more than whole composition 65wt%.
16. the described composition of claim 14 comprises and accounts for the polysiloxane intermediate of whole composition 0.5wt% to 35wt%.
17. the described composition of claim 14, wherein catalyzer is selected from organometallic compound, amine compound, acid, alkali and composition thereof.
18. the described composition of claim 17, wherein catalyzer is the mixture of organometallic compound and amine compound.
19. the described composition of claim 18, wherein organometallic compound is the organo-tin compound with following general formula:
R wherein
8, R
9, R
10And R
11Respectively be selected from the alkyl of 11 carbon atoms at the most, aryl, aryloxy, and alkoxyl group, and R
8, R
9, R
10And R
11In any two also optional self-contained halogens, the inorganic atoms of sulphur and oxygen.
20. the described composition of claim 18, wherein amine compound has following general formula:
R wherein
12And R
13Respectively be selected from hydrogen, the aryl and the alkyl of 12 carbon atoms at the most, and R
14Be selected from the alkyl of 12 carbon atoms, aryl and hydroxyalkyl at the most.
21. the described composition of claim 14 comprises and accounts for the catalyzer of whole composition 5wt% to 25wt%.
22. the mixture with resin Composition, this resin Composition comprise the composition according to claim 14 preparation.
23. a phenolic siloxane composition, by mixing following component preparation:
A kind of resol;
A kind of polysiloxane intermediate; With
A kind of said composition that promotes is processed and the solidified catalyzer being lower than under 100 ℃ the temperature, wherein the reaction of resol and polysiloxane intermediate generates the interpenetrating(polymer)networks of siloxane polymer and novolac polymer, wherein the main chain of novolac polymer comprise the Si-O group and wherein said composition comprise and account for the above resol of the about 65wt% of whole compositions.
24. the described composition of claim 23, the wherein not siliceous solids of said composition.
25. the described composition of claim 23 comprises and accounts for the polysiloxane intermediate of whole composition 0.5wt% to 35wt%.
26. the described composition of claim 23, wherein catalyzer is selected from organometallic compound, amine compound, acid, alkali and composition thereof.
27. the described composition of claim 26, wherein catalyzer be the mixture of a kind of organometallic compound and a kind of amine compound and wherein said composition comprise and account for whole compositions catalyzer of 10wt% at the most.
28. the mixture with resin Composition, this resin Composition comprise the composition according to claim 23 preparation.
29. a phenolic siloxane composition, by mixing following component preparation:
A kind of novolac;
A kind of formaldehyde donor;
A kind of polysiloxane intermediate; With
A kind of promotion comprises the catalyzer of the thermoset interpenetrating polymer networks formation of siloxane polymer and novolac polymer, wherein has the Si-O group on the novolac polymer main chain.
30. the described composition of claim 29, the wherein not siliceous solids of said composition.
31. the described composition of claim 29 comprises and accounts for the polysiloxane intermediate of whole composition 0.5wt% to 35wt%.
32. the described composition of claim 29, wherein catalyzer is selected from organometallic compound, amine compound, acid, alkali and composition thereof.
33. the described composition of claim 32, wherein catalyzer is the mixture of a kind of organometallic compound and a kind of amine compound.
34. the described composition of claim 33, wherein organometallic compound is the organo-tin compound with following general formula
R wherein
8, R
9, R
10And R
11Respectively be selected from the alkyl of 11 carbon atoms at the most, aryl, aryloxy, and alkoxyl group, and R
8, R
9, R
10And R
11In any two also optional self-contained halogens, the inorganic atoms of sulphur and oxygen.
35. the described composition of claim 33, wherein amine compound has following general formula
R wherein
12And R
13Respectively be selected from hydrogen, the aryl and the alkyl of 12 carbon atoms at the most, and R
14Be selected from alkyl, aryl and the hydroxyalkyl of 12 carbon atoms at the most.
36. the described composition of claim 29 comprises and accounts for the catalyzer of whole composition 5wt% to 25wt%.
37. the mixture with resin Composition, this resin Composition comprise the composition according to claim 29 preparation.
38. a thermosetting phenolic silicone composition, by mixing following component preparation:
A kind of novolac;
A kind of formaldehyde donor;
A kind of polysiloxane intermediate; With
Capacity promotes said composition being lower than the catalyzer that is cured under 100 ℃ the temperature, novolac wherein, formaldehyde donor, reaction generates interpenetrating polymer networks with the polysiloxane intermediate, wherein the resol main chain comprise the Si-O group and wherein said composition comprise and account for the above novolac of the about 50wt% of whole compositions.
39. the described composition of claim 38 comprises and accounts for the polysiloxane intermediate of whole composition 0.5wt% to 35wt%.
40. the described composition of claim 38, wherein catalyzer is selected from organometallic compound, amine compound, acid, alkali and composition thereof.
41. the described composition of claim 40, wherein catalyzer be the mixture of a kind of organometallic compound and a kind of amine compound and wherein said composition comprise and account for whole compositions catalyzer of 10wt% at the most.
42. the mixture with resin Composition, this resin Composition comprise the composition according to claim 38 preparation.
43. the multiple-unit tube with resin Composition, this resin Composition comprise by following component and mix and the phenolic siloxane composition of preparation:
A kind of resol;
A kind of polysiloxane intermediate; With
Capacity promotes the solidified catalyzer, and wherein the reaction of resol and polysiloxane intermediate generates the interpenetrating polymer networks of siloxane polymer and novolac polymer.
44. one kind by whipping agent, the foam that tensio-active agent and phenolic siloxane composition are made, and said composition prepares by mixing following component:
A kind of resol;
A kind of polysiloxane intermediate; With
Capacity promotes said composition solidified catalyzer, and wherein the reaction of resol and polysiloxane intermediate generates the interpenetrating polymer networks of siloxane polymer and novolac polymer.
45. one kind prepares the phenolic siloxane method for compositions, may further comprise the steps:
The phenol component mixed forming mixture with the polysiloxane intermediate, wherein exist in this mixture silanol and with the phenol component in hydroxyl reaction and wherein silanol and other silanol reaction generation siloxane polymer; With
Add the aldehyde component to generate novolac polymer in this mixture, wherein composition comprises the interpenetrating polymer networks of being made up of novolac polymer and siloxane polymer.
46. one kind prepares the phenolic siloxane method for compositions, comprises the steps:
Resol is mixed the formation mixture with the polysiloxane intermediate, this mixture comprises silanol, phenolic hydroxyl group and phenol methylol hydroxyl;
Allow at least a reaction in silanol group and phenolic hydroxyl group and the phenol methylol hydroxyl; With
In this mixture, add the capacity catalyzer to promote mixture solidified.
47. the described method of claim 46 comprises that mixture thus forms the interpenetrating polymer networks of novolac polymer and siloxane polymer.
48. one kind prepares the phenolic siloxane method for compositions, may further comprise the steps:
Novolac is mixed the formation mixture with formaldehyde donor and polysiloxane intermediate, this mixture comprises silanol and phenolic hydroxyl group;
Make the reaction of silanol group and phenolic hydroxyl group; With
In mixture, add the capacity catalyzer to promote curing.
49. the described method of claim 48 comprises the interpenetrating polymer networks that is formed novolac polymer and siloxane polymer by this mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96194806A CN1187836A (en) | 1995-04-21 | 1996-04-19 | Phenolic resin compositions with improved impact resistance |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/426,245 | 1995-04-21 | ||
| CN96194806A CN1187836A (en) | 1995-04-21 | 1996-04-19 | Phenolic resin compositions with improved impact resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1187836A true CN1187836A (en) | 1998-07-15 |
Family
ID=5128834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96194806A Pending CN1187836A (en) | 1995-04-21 | 1996-04-19 | Phenolic resin compositions with improved impact resistance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1187836A (en) |
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| CN100419009C (en) * | 2006-03-13 | 2008-09-17 | 覃强 | Process for producing phenolic foam capable of improving flame-retarding property |
| CN102887916A (en) * | 2012-09-29 | 2013-01-23 | 中昊晨光化工研究院有限公司 | Alkoxy silicon resin intermediate and preparation method thereof |
| CN102942662A (en) * | 2012-09-25 | 2013-02-27 | 山东圣泉化工股份有限公司 | Preparation method of phenolic resin for refractory material |
| WO2013076744A1 (en) * | 2011-11-21 | 2013-05-30 | Freni Brembo S.P.A | Material for friction components of disc brakes |
| CN103601892A (en) * | 2013-11-28 | 2014-02-26 | 中国科学院长春应用化学研究所 | Silicone rubber and preparation method thereof |
| CN105647108A (en) * | 2016-03-30 | 2016-06-08 | 西安交通大学 | Siloxane-modified phenolic resin for hot melt preimpregnation technology and preparation method of siloxane-modified phenolic resin for hot melt preimpregnation technology |
| CN107923463A (en) * | 2015-08-13 | 2018-04-17 | 舍弗勒技术股份两合公司 | Chemically activated friction material |
| CN110199002A (en) * | 2016-12-22 | 2019-09-03 | 圣戈班磨料磨具股份有限公司 | Abrasive product and forming method thereof |
| CN112210079A (en) * | 2020-10-23 | 2021-01-12 | 中国科学院化学研究所 | Silicon hybrid phenolic resin and synthetic method thereof |
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1996
- 1996-04-19 CN CN96194806A patent/CN1187836A/en active Pending
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| CN100419009C (en) * | 2006-03-13 | 2008-09-17 | 覃强 | Process for producing phenolic foam capable of improving flame-retarding property |
| US10302164B2 (en) | 2011-11-21 | 2019-05-28 | Freni Brembo S.P.A. | Material for friction components of disc brakes |
| WO2013076744A1 (en) * | 2011-11-21 | 2013-05-30 | Freni Brembo S.P.A | Material for friction components of disc brakes |
| CN104040209A (en) * | 2011-11-21 | 2014-09-10 | 福乐尼·乐姆宝公开有限公司 | Material For Friction Components Of Disc Brakes |
| CN104040209B (en) * | 2011-11-21 | 2020-11-10 | 福乐尼·乐姆宝公开有限公司 | Material for friction assembly of disc brake |
| CN102942662A (en) * | 2012-09-25 | 2013-02-27 | 山东圣泉化工股份有限公司 | Preparation method of phenolic resin for refractory material |
| CN102887916A (en) * | 2012-09-29 | 2013-01-23 | 中昊晨光化工研究院有限公司 | Alkoxy silicon resin intermediate and preparation method thereof |
| CN102887916B (en) * | 2012-09-29 | 2016-03-02 | 中昊晨光化工研究院有限公司 | A kind of Alkoxy silicon resin intermediate and preparation method thereof |
| CN103601892A (en) * | 2013-11-28 | 2014-02-26 | 中国科学院长春应用化学研究所 | Silicone rubber and preparation method thereof |
| CN103601892B (en) * | 2013-11-28 | 2016-01-06 | 中国科学院长春应用化学研究所 | A kind of silicon rubber and preparation method thereof |
| CN107923463A (en) * | 2015-08-13 | 2018-04-17 | 舍弗勒技术股份两合公司 | Chemically activated friction material |
| CN105647108A (en) * | 2016-03-30 | 2016-06-08 | 西安交通大学 | Siloxane-modified phenolic resin for hot melt preimpregnation technology and preparation method of siloxane-modified phenolic resin for hot melt preimpregnation technology |
| CN110199002A (en) * | 2016-12-22 | 2019-09-03 | 圣戈班磨料磨具股份有限公司 | Abrasive product and forming method thereof |
| CN112210079A (en) * | 2020-10-23 | 2021-01-12 | 中国科学院化学研究所 | Silicon hybrid phenolic resin and synthetic method thereof |
| CN113337075A (en) * | 2021-04-29 | 2021-09-03 | 山东宇世巨化工有限公司 | Two-component polysiloxane modified phenolic resin and preparation method thereof |
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