CN103360728B - Phosphorus-containing copolyester foam combined material and method for preparing phosphorus-containing copolyester foam by adopting phosphorus-containing copolyester foam combined material - Google Patents
Phosphorus-containing copolyester foam combined material and method for preparing phosphorus-containing copolyester foam by adopting phosphorus-containing copolyester foam combined material Download PDFInfo
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- CN103360728B CN103360728B CN201210083654.6A CN201210083654A CN103360728B CN 103360728 B CN103360728 B CN 103360728B CN 201210083654 A CN201210083654 A CN 201210083654A CN 103360728 B CN103360728 B CN 103360728B
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- 0 *CC(*)C[P@@](C1=CC=N)(OC2C=C*C=C[C@]2C1=CC=C)=O Chemical compound *CC(*)C[P@@](C1=CC=N)(OC2C=C*C=C[C@]2C1=CC=C)=O 0.000 description 1
- FNTPQIFPIPMIPI-UHFFFAOYSA-N CC(Oc(cc1)cc(P2(Oc(cccc3)c3-c3c2cccc3)=O)c1OC(C)=O)=O Chemical compound CC(Oc(cc1)cc(P2(Oc(cccc3)c3-c3c2cccc3)=O)c1OC(C)=O)=O FNTPQIFPIPMIPI-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a phosphorus-containing copolyester foam combined material and a method for preparing phosphorus-containing copolyester foam by adopting the combined material. The phosphorus-containing copolyester foam combined material is prepared from the following constituents in parts by weight: 100 parts of phosphorus-containing copolyester, 0.1-20 parts of a tackifier, 0.1-20 parts of a foamer and 0-10 parts of a nucleant; the phosphorus content of the phosphorus-containing copolyester is 10-20000 ppm, and the IV (inherent viscosity) value of the phosphorus-containing copolyester is 0.40-1.40dL/g. The phosphorus-containing copolyester foam is obtained from the phosphorus-containing copolyester foam combined material via a one-step method or a two-step method. The phosphorus-containing copolyester foam is excellent in fireproof performance and capable of meeting the class requirements of class-B burning behaviour in the standards of classification for burning behaviour of building materials and products, and has an oxygen index greater than 30%; and the phosphorus-containing copolyester foam combined material can be used as a sandwich foam core material (for rail traffic, vehicles, aviation, ships, industry, furniture and the like) with high fireproof requirements, and a material with building structural property and double functions of heat isolation and warm preservation.
Description
Technical field
The present invention relates to a kind of phosphorous copolyester foam composition material and adopt this premixed systems to prepare the method for phosphorous copolyester foam, this phosphorous copolyester foam has excellent fire resistance, and the B level burning behavior class requirement of " material of construction and product burns grading performance " standard can be met, oxygen index is greater than 30%, can be used as the sandwich foam core material (as track traffic, vehicle, aviation, boats and ships, industry and furniture etc.) of high fire protection requirement and building structure and heat-insulation and heat-preservation bifunctional material.
Background technology
Polyester belongs to combustible material, its time, the phenomenons such as heat release rate is large, calorific value is high, flame propagation speed, melting drippage, this characteristic makes it still receive certain restriction in the application of some key areas (as track traffic, transport, building, electron device, the vehicles, health care etc.).
Since nineteen seventies, the fire-retardant investigation and application exploitation of countries in the world to polyester becomes increasingly active, and the modification of flame retardant type polyester is mainly taked to add wherein as the fire retardant such as halogen and phosphorus compound.Existing research shows, containing halogen element, although particularly the fire retardant of chloride, bromine is comparatively effectively and be widely used, but time easily discharge pungency and corrosive gas, as hydrogen halide, dioxin etc., people is sucked and suffocates, thus be also that the application of halogen containing flame-retardant is restricted; Existing research shows, phosphorus is one of the most effective polyester flame-retardant element (Wang Yuzhong work, the flame-retarded design of trevira, Sichuan Science Press, 1994).Phosphorus flame retardant pyrolysis when being heated is phosphoric acid, is finally converted into poly-metaphosphoric acid or the tetra-sodium class product of vitreous state, forms sealing coat at material surface, stops heat trnasfer, reduces inflammable gas burst size and isolated air, reaches fire-retardant object.Certainly, fire retardation is difficult to be realized by certain single fire retardant mechanism, usually shows as the comprehensive coordination effect of number of ways.
For the flame resistant method of polyester and trevira, by the feed postition of production process and fire retardant, following several mode can be divided into:
(1) blending fire retardant modification: add fire retardant to polyester system, do not change polyester production process;
(2) fire retardant is grafted polyester modified: on trevira or fabric, make itself and reactive flame retardant generation Surface grafting reaction reach fire-retardant object;
(3) flame-retardant after-finishing: fabric is placed in fire resistant fluid and floods the regular hour, takes out and dries.
(4) conjugate spinning is flame-retardant modified: carry out conjugate spinning with conventional polyester and the polyester containing flame-retardant composition.
(5) copolymerization is flame-retardant modified: add reactive flame retardant in esterification or polycondensation phase and carry out copolycondensation.
Blending fire retardant modification, can affect the persistence of flame retardant properties, and in addition, fire retardant easily oozes out, and can produce harmful effect to human body and environment.Fire retardant is grafted polyester modified and conjugate spinning is flame-retardant modified, and technical qualification are high, and cost is also higher, and equipment is complicated, is not easily generally used.Flame-retardant after-finishing, lack durability of fire-retardant, and larger impact is produced on the feel of fabric, intensity, ventilation property and color and luster etc., copolymerization is flame-retardant modified, because copolyreaction type phosphorus fire retardant has hydroxyl, carboxyl Liang Ge functional group, can join in the molecular chain of polyester with alcohol, acid-respons, give polyester good flame retardant properties from molecular chain structure, and durability of fire-retardant be desirable.To sum up, phosphorous copolyester is the flame retardant polyester technology of inherently giving polyester good flame-retardance energy of current scientific circles and industry member accreditation.
Each company adopts the difference of the flame-retardant monomer of different structure formula, the reactant of different activities, different polymerizing conditions and polymerization methods to prepare phosphorous copolyester, flame retardant effect is also not quite similar, and main influence factor is the structure of flame-retardant monomer and the structure of phosphorous copolyester.
Chinese patent CN201010284925.5 discloses a kind of high-molecular weight phosphorous flame retardant random copolyester and preparation method, and this atactic polyester general structure is as follows:
In formula, A is the repeated structural unit of phosphor-containing flame-proof monomer, m and n is positive integer, and the intrinsic viscosity of this atactic polyester is 1.2-2.2dL/g, preferred 1.4-2.2dL/g, the content of the repeated structural unit of phosphor-containing flame-proof monomer is the 1-30% of this copolyesters repeated structural unit total mass.
In this atactic polyester, the repeated structural unit A of phosphor-containing flame-proof monomer is at least one in following structure:
In formula, R
1for containing C
1-C
8alkyl or phenyl or benzyl, R
2and R
3for C
1-C
8alkylidene group or aryl, the two can identical also can not be identical; X, Y and Z are O atom.The limiting oxygen index(LOI) of this phosphorous atactic polyester can reach 33%, on the basis with excellent flame retardant performance, also improves its corresponding mechanical property, can be widely used in and manufacture film, bottle class, protective clothing, tent, even fire-retardant high-strength industrial yarn.
US Patent No. 5602212 and US4981945 also disclose a kind of phosphorous linear copolyester, and the repeated structural unit of its phosphor-containing flame-proof monomer is also the one in said structure.
Chinese patent CN201010602958.X discloses the fire-retardant Thermotropic Liquid of a kind of novel low-melting point phosphor-containing nitrogen, this copolyesters is atactic polyester, its phosphorous-containing monomers is 10-(2,5-dihydroxy phenyl) diacetate esters (ODOPB) of-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, structural formula is as follows:
Chinese patent CN201010567685.X discloses the fire-retardant blocked copolyester of a kind of phosphorous Poly(Trimethylene Terephthalate), and contained by it is at least one in following phosphorous glycol containing phosphorus component:
Or at least one of the phosphorous diacid diol ester to obtain through esterification for following phosphorous diacid and ethylene glycol or 1,3-PD or BDO:
Or be the mixture of any one in above-mentioned phosphorous glycol in any one and phosphorous diacid diol ester.The oxygen index of the fire-retardant blocked copolyester prepared by method can up to 33%.
Chinese patent CN200810045357.6 discloses a kind of phosphoric flame-proof copolyester ionomer and preparation method thereof, and its flame-retardant monomer used is the compound with following general structure:
In formula, R
1for C
1-C
12alkyl, aryl or benzyl; R
2for C
1-C
8alkylidene group or aryl; X is O atom,
Or for the assorted-10-of 9, the 10-dihydro-9-oxies with following general structure acyl of seeing is mixed luxuriant and rich with fragrance compounds:
In formula, R
3for propane-1，2，3-triyl, Y is O atom, Z
1, Z
2for hydroxy-acid group or ester group group, Z
1, Z
2can be identical, also can not be identical.
Chinese patent CN200910059955.3 discloses a kind of phosphorous and kinking groups thermotropic liquid crystal random copolyester, and its phosphor-containing structure unit forms as necessity, and structure is as follows:
Chinese patent CN200910058655.3 discloses a kind of preparation method of phosphorus series non-halogen flame-proof copolyester, mate by raw material and technique the requirement that the fire-retardant rank of phosphorus series non-halogen flame retardant polyester polymer product obtained can reach the high flame retardant such as 94UL V-0 level or VTM-0 level film, limiting oxygen index(LOI) (LOI) is up to more than 45%.Can be used as the raw material that production flame retardant properties reaches 94UL V-0 level or VTM-0 (being referred to as V0 level) film, fire-retardant I level and above fire-retardant fibre and V0 level flame retardant plastics goods.Halogen-free phosphorus-containing copoly type fire retardant described in it is the compound with following formula:
In formula, R is C
1-C
15fisher's formula or cyclic alkyl, R ' is alkyl (C
1-C
5) or C
6-C
9aryl or benzyl.
Chinese patent CN00135411.6 discloses a kind of conveniently blended processing phosphor-containing flame-proof polyester and goods thereof and in the raising phosphorous copolyester taked, phosphorus content prepares the manufacture method of the high-concentration phosphorus-contained copolyester as fire-retardant master granule.The molecular formula of its phosphorous organic reaction type fire retardant is:
In formula, R
1: C
1-C
6alkyl or C
6-C
9aryl; R
2: C
1-C
6alkylidene group; R
3: H, C
1-C
6alkyl or the hydroxyalkyl of correspondence; R
4: H, C
1-C
6alkyl or the hydroxyalkyl of correspondence.US Patent No. 5602212 also discloses a kind of phosphorous linear copolyester, its
US Patent No. 4214069 discloses a kind of high molecular phosphor-containing flame-retardant copolyester, and the general structure of the phosphorus unit that it contains is as follows:
In formula, R
1, R
2for H atom or C
1-C
18fisher's formula or cyclic alkyl, R
1, R
2can be identical, also can not be identical; R
3for functional group's group that can form ester group (has following structural formula :-COOR
5or-OR
5, wherein R
5for H atom or the C at least containing a hydroxyl
1-C
12alkyl); A
1for C
1-C
12alkylidene group.
US Patent No. 04737567 discloses a kind of phosphorous atactic polyester, and its phosphorous repeat unit structure is as follows:
In formula, Ar
1represent 3 valency aromatic groups, being H atom or the alkyl group of 1-20 carbon atom or the aromatic alkyl group of alkoxy grp or 6-20 carbon atom or aralkyloxy groups, such as, can be following phosphor-containing flame-proof monomer:
US Patent No. 5650531 discloses a kind of high content of phosphorus halogen-free flameproof oligopolymer and preparation method thereof.Described P contained compound has following general formula:
In formula, R is alkyl group or phenyl, naphthyl and the biphenyl group of 1-10 carbon atom; A can be-R or-OR.
US Patent No. 4157436 discloses a kind of phosphor-containing flame-retardant copolyester, and the general structure of its phosphorous organic reaction type fire retardant is as follows:
R in formula
1for the alkyl group with hydroxyl of H atom or 1-10 carbon atom; R
2and R
3for the alkyl group of halogen atom or 1-10 carbon atom; M and n represents the integer of 0-4.Concrete molecular formula can be following:
Also have and introduce nitrogen element or phenyl raising flame retardant effect on phosphorus flame retardant.As Chinese patent CN200580014834.7 discloses a kind of nitrogenous phosphorus flame retardant, Chinese patent CN200410084108.X discloses a kind of response type phosphorus fire retardant containing phenyl, and what use in Chinese patent CN02109909.X is also containing phenyl phosphorus fire retardant.Chinese patent CN200810023617.X discloses that a kind of PET hue of production is good, the preparation method with the flame-retarding phosphorus copolymerized polyester of good form and aspect of excellent fireproof performance.Its phosphorus flame retardant used is the one or more than one with following 3 kinds of general structures:
Wherein R
1for alkyl group or the alkoxy grp of nitrogen-containing group or 1-15 carbon atom, R
2for the alkyl group of 1-9 carbon atom, R
3and R
4represent alkyl group or the alkoxy grp of 1-15 carbon atom, m and n represents the integer of 0-4, when m is the integer of 2-4, there is multiple R
3can be same to each other or different to each other; When n is the integer of 2-4, there is multiple R
4can be same to each other or different to each other; A represent containing ester linkage containing the alkyl group of 3-6 carbon atom or alkoxy grp.
In addition, the class phosphonium flame retardant that US Patent No. 4587362, US4358045 and US4088205 also use Spirocyclic prepares phosphorous copolyester, and be mainly used in the fire-retardant of dacron fabric, the structural formula of its fire retardant is as follows:
In sum, phosphorus system reactive flame retardant mainly contain phosphorus at main chain and phosphorus two kinds of forms on side chain, using at present more is backbone chain type phosphorus fire retardant.Flame-proof copolyester can be random, block, grafting or alternately flame-proof copolyester.
The oxygen index of the phosphorous copolyester resin that above-mentioned patent system is standby is at least 25%, what have can up to 45%, much larger than the oxygen index about 21% of conventional polyester, but, the vibrin of effective flameproof effect and limited range of application is achieved, the aspect application such as such as fiber, film, bottle class and Fire Retardant Industry silk in above patent.But these have the low extrusion foaming that can not directly should be used for of vibrin melt viscosity of flameproof effect, thus these patents also have no requirement and cover foam materials range of application.
Due to general purpose grade polyester, the melt viscosity as terephthalic acid hexylene glycol ester (PET) and phosphorous copolyester is low, can not become desirable foam materials for abscess during extrusion foaming easily breaks.Research afterwards finds by using suitable coupling agent can connect side chain and then improve molecular weight and melt viscosity thereof on linear molecular chain.This development makes to produce thermoplastic polyester foam by extrusion and foaming process becomes possibility.Branching coupling agent is the chemical substance containing multiple reactive functionality, can carry out condensation reaction with plural molecular chain and produce branched chain polymer.Melt extrude branched chain polyester and suitable chemistry, physics or inert gas blown agent can make unicellular structure foam.
US Patent No. 522932 discloses a kind of method of polyester extrusion foaming, in polycondensation process, adds the branching agent that reactive functionality is greater than 2.The usage quantity of branching agent is in 1.5-6 equivalent concentration of every 100 mole of diacid.By polycondensation, the PET resin of branching is formed.Then this branched resin is used to carry out extrusion foaming.
US Patent No. 4132707 and US5422381 etc. disclose a kind of method of polyester extrusion foaming, adopt for general purpose grade and the PET resin reclaiming level, melt extrude and give blended method first by resin and the granulation of branching agent Homogeneous phase mixing.Then solid particulate be heated under vacuum or nitrogen protection 170-220 DEG C then holding temperature complete solid-state branching reaction to certain hour.PET resin through solid-state upgrading reaction preparation can be used for carrying out extrusion foaming.
US Patent No. 5000991 discloses a kind of use branching agent and general purpose grade or reclaims level PET resin melt blending in an extruder, then directly adds the method for whipping agent extrusion foaming at same machine back segment.The course of processing can be reduced in this way, equipment investment and production time.But the reaction efficiency of branching agent does not have first two method high, and in froth product, the content of residual branching agent is also higher, and these residues seriously reduce the fire resistance of foam.In order to improve this technological process, US Patent No. 5696176 branching agent mother material is developed.Mother material uses polyethylene or polypropylene to make masterbatch as the branching agent of carrier and high density is blended, then uses this masterbatch and general purpose grade or reclaim the common extrusion foaming of level PET resin.
Chinese patent CN200910302063.1 discloses a kind of method utilizing bottle level PET foaming to prepare PET sheet, it improves PET melt viscosity and intensity by the means of adding the acrylate multipolymer of polyfunctional group high active substance and nucleocapsid structure, add chemical foaming agent, prepare the PET sheet that thickness is 0.8-1.5mm, this PET sheet is suitable for manufacturing food, medicine and electronic pallet etc.
Chinese patent CN99812803.1 discloses a kind of method of PET foam article, adopt epoxy group(ing) coupling agent improve the PET type resin with lower molecular weight and fragility, the polyester particularly reclaimed molecular weight and improve its melt strength and swellingly to prepare.This foam article can be used as cushioning material, insulating material, wrapping material, food product containers and dispensing materials etc.
Chinese patent CN98804872.8 also discloses polyester foamed method and the foam of preparation.Be at least 0.8dl/g by extrusion molding intrinsic viscosity and add whipping agent polyester raw material realize.This expanded polyester is such as the manufacture of the plate, thin plate and the pipe that particularly use in building and encapsulation field.
Chinese patent CN 200980121758.8, disclose a kind of pre-composition adding thermoplastic elastomer and tetracarboxylic dianhydride in vibrin, and being foamed into foams, this foam contains the thermoplastic polyester elastomer that 0.5-15 weight is made a gesture of measuring, and the tear type variable of polyester form is increased.
Sandwich structure composite material is the particular design body that low-density core and the thin skin with high tensile are combined into.This structure is successfully applied requiring lightweight, planar strength and the high industrial circle of rigidity, as ships and light boats waterborne, aircraft, spacecraft, transportation and communication and other general industrial application.Sandwich structure composite material has specific function so to be because low-density core significantly improves the relative rigidity of skin material after combining with skin material, and the weight increase of unit surface is very little.By selecting suitable skin material and the combination of core, weight is that 3% core of skin material weight can improve flexural strength 3.5 times and bending stiffness 7 times respectively.
People are the most often compared to sandwich structure composite material the I-beam of repetition.Its skin material is equivalent to the upper and lower plates of brigade beam, and core is equivalent to the muscle of I-beam.When it is subject to load, power passes to another side from one side through core.The power that core is subject to has pressure, draws and shearing force.The bending stiffness of sandwich structure composite material is directly proportional to the thickness of core, just as the rigidity of I-beam is directly proportional the same with the distance between its upper and lower plates.When matrix material core thickness doubles, its flexural strength increases by six times, and bending stiffness increases twelvefold.
In core filled composite material, the over-all properties of core is extremely important.The ideal performance of core comprises high strength and stiffness, low density, good chemically-resistant solvent and thermotolerance and low price etc.A core performance in actual applications can be predicted by carrying out laboratory test to it.These tests comprise compression, stretch and shearing test, and its performance index comprise intensity, modulus and anamorphic stretching rate etc.In the industry of structure sandwich material, the most frequently used core has cork wood, honeycomb structure core, thermoplasticity and thermosetting foams core etc.
But the polyester form made by above-mentioned patent process is usually unsuitable for doing sandwich material, because its foam aperture is too large, and pore size distribution is wide too, which results in poor mechanical property.In the foaming process that above-mentioned patent provides, the extrusion die that the polyester fondant being mixed with the collateralization of volatile organic blowing agent or rare gas element is extruded through an annular or slit opening enters in atmospheric environment.In atmospheric pressure state, whipping agent expanding polyurethane melt and become foamy structure.As produced the thickness reaching conventional sandwich material requirement, then overplumping makes the abscess-size of foamed products excessive by whipping agent, the problems such as the even irregular surface of skewness.
US Patent No. 7951449 discloses a kind ofly extrudes the method preparing polyester form sandwich material, and the application of the foam core material of preparation.Its die head is not slit or ring-type die orifice, but foraminous die plate.Hole in template, by uniform sequential those bubble bars extruded by them consistent of arranging, is merged mouth mould boundling technology by bar bubble, can be combined the cystose then melted as without any space closely.This section of patent makes PET become possibility as sandwich structure material, and first pushed market by 3A company in 2005, the foam core material manufacturers that a few family is important in the world such as Sweden DIAB, Switzerland GURIT and Belgian Armacell have also released one after another respective PET foam core material obtain corresponding market, as the field such as wind electricity blade and track traffic.
Polyester construction foam has the microvoid structure of trickle abscess, desirable dimensional stability, thermostability, chemical stability, excellent mechanical mechanics property, barrier property (heat-insulation and heat-preservation), antiultraviolet, water-absorbent is low, and its environmental friendliness, be easy to recycling.Just because of above-mentioned good characteristic, conventional polyester foam is widely used in packaging field (food, medicine, electronics etc.).PET structure sandwich foam materials is at industrial circle (sports equipment, freight container etc.), field of track traffic (floor, engine shield etc.), boats and ships (deck, internal structure etc.), the fields such as wind energy (blade, engine room cover etc.) and building obtain good application.But above-mentioned foam does not have, or only there is lower fire resistance, substantially do not reach the fire protection requirement of China's building industry.
Current China is newly-increased floor area of building about 2,000,000,000 square metres every year, and wherein the completed floor space of building curtain wall is 7,500 ten thousand square metres.Building curtain wall is sandwich structure composite sheet substantially, uses sandwich material area to be 2,250 ten thousand square metres, estimates that 2012 annual requirements will reach about 6000 tons.Huge newly-increased construction amount and reconstruction of existing building are that New Building Materials development provides the wide market space.Existing heat-insulating material mainly comprises: EPS, XPS, urethane, rock wool, glass wool, plank, foamed concrete etc.Can not reasonably unification in environmental-protecting performance, mechanical property, processing characteristics, heat-insulating property, fire resistance, weather resistance and application property etc., respective relative merits are obvious.Light foam lagging material wherein does not all reach desirable fire protection requirement.
Along with people's level of consumption, building industrialization level and building energy conservation requirement etc. improve day by day, the enhancing day by day of environmental consciousness, the concept day of low-carbon emission reduction enters the popular feeling, requires that New Building Materials are to safety, environmental protection, energy-conservation, waterproof, high-quality, the complex function future development such as attractive in appearance.Structure-type construction wall and the parts of making the energy-conserving and environment-protective integrating the several functions such as fire prevention, antidetonation, insulation, waterproof, noise reduction, decoration with structural foam sandwich material have become a kind of development trend.Such as with the energy saving building curtain wall that sandwich material is made, can wall weight be alleviated, improve the effect that wall thermal insulating is heat insulation, and there is good sound insulation, fire-retardant and erosion resistance.Additionally by adjust structure, it also can be used as materials for wall, the such as body of wall in house inner wall and rapid-assembling room, these rapid-assembling rooms may be used for disaster relief and rescue, building site barracks, also will be conducive to builder and build general house faster, this has subversive meaning at building materials field.
Market generally believes that polyester construction foam core material can be used as at building field being incubated the type material be combined with mechanical property, can substitute above-mentioned existing high-strength, lightweight, heat insulation, fire-retardant material for building.Polyester construction foam core material uses as building, and precondition must meet Building Fire Protection requirement.Commercially available stagnant combustion, the polyester construction foam core material of low cigarette, just meet the requirement about fire resistance of the DIN5510 of field of track traffic, but its oxygen index only has about 26%, do not reach the requirement that fire-retardant rank, i.e. oxygen index are not less than 28%, just substantially limit it has high fire protection requirement field application in building etc.
To sum up, (1) has the low extrusion foaming that can not directly be used for of phosphorous copolyester resin melt viscosity of flameproof effect, and it can only be applied in such as fiber, film, bottle class and Fire Retardant Industry silk etc.; (2) even if current polyester form product adds fire retardant in preparation process, also can not meet the application requiring that oxygen index is not less than 28%.
Summary of the invention
For solving the problem, applicant has carried out a large amount of further investigations to phosphorous copolyester, find after deliberation, the phosphorous copolyester simultaneously met the following conditions may be used for preparing phosphorous copolyester foam: 1) phosphorus content of phosphorous copolyester is 10-20000ppm, preferred 5000-18000ppm; 2) the IV value of phosphorous copolyester is 0.40-1.40dL/g.
Based on above-mentioned research, the present invention proposes a kind of phosphorous copolyester foam composition material, and adopt this premixed systems to prepare the method for phosphorous copolyester foam, this phosphorous copolyester foam has excellent fire resistance, and the B level burning behavior class requirement of " material of construction and product burns grading performance " standard can be met, oxygen index is greater than 30, can be used as the sandwich foam core material (as track traffic, vehicle, aviation, boats and ships, industry and furniture etc.) of high fire protection requirement and building structure and heat-insulation and heat-preservation bifunctional material.
Phosphorous copolyester foam composition material of the present invention is prepared from by following components by weight parts number ratio: 100 portions of phosphorous copolyesters, 0.1-20 part tackifier, 0.1-20 part whipping agent and 0-10 part nucleators.The phosphorus content of above-mentioned phosphorous copolyester is 10-20000ppm, preferably 5000-18000ppm; IV value is 0.40-1.40dL/g.IV value is bad lower than foaming effect during 0.40dL/g, and higher than 1.40dL/g, then cost is too high.
Above-mentioned phosphorous copolyester can be pure phosphorous copolyester, also can be the blend of phosphorous copolyester and conventional polyester (can be the mixture of the arbitrary proportion of PET, PBT, PTT, PEN, PCT and their multipolymer or more polyester).In this blend, the weight content of phosphorous copolyester is 25% ~ 100%.
Above-mentioned phosphorous copolyester can be phosphorous PET (polyethylene terephthalate) copolyesters, phosphorous PBT (polybutylene terephthalate) copolyesters, phosphorous PTT (Poly(Trimethylene Terephthalate)) copolyesters, phosphorous PEN (PEN) copolyesters, phosphorous PCT (poly terephthalic acid 1,4-cyclohexane dicarboxylates) mixture of copolyesters or their arbitrary proportions, preferred phosphorous PET copolyesters.
Above-mentioned phosphorous copolyester can be random copolymers, segmented copolymer, graft copolymer or alternating copolymer.
Above-mentioned phosphorous copolyester can be the mixture of phosphor-containing flame-proof PET copolyesters, phosphor-containing flame-proof PBT copolyesters, phosphor-containing flame-proof PEN copolyesters or their arbitrary proportions, preferred phosphor-containing flame-proof PET copolyesters.
Above-mentioned phosphorous copolyester refers to the copolyesters obtained by response type P contained compound participation copolycondensation, and this phosphorous copolyester comprises polyester phosphorous in polyester phosphorous in main chain and side chain.For polyester phosphorous in main chain, wherein response type P contained compound is the compound with following general structure:
In formula: R
1for nitrogen-containing group or C
1-C
12alkyl, aryl or benzyl; R
2for H or C
1-C
6alkyl or the hydroxyalkyl of correspondence; R
3for C
1-C
8alkylidene group or aryl; W is oh group, hydroxy-acid group or ester group group.Such as:
deng;
Or for having the compound of following general formula:
Such as:
deng;
Or be such as:
Deng Spirocyclic P contained compound.
For polyester phosphorous in side chain, wherein response type P contained compound is that the acyl of seeing of the assorted-10-of 9,10-dihydro-9-oxies with following general structure is mixed luxuriant and rich with fragrance compounds:
In formula, R
4for nitrogen-containing group or C
1-C
8alkyl, aryl; R
5and R
6for C
1-C
15alkyl group or alkoxy grp; Y
1, Y
2for H, hydroxy-acid group, hydroxyl or ester group group, Y
1, Y
2can be identical, also can not be identical, Y
1, Y
2cannot be H simultaneously.M and n is the integer of 0-4.Such as:
Polyester phosphorous in the preferred main chain of above-mentioned phosphorous copolyester.
The tackifier that described tackifier can be chainextender or 0.1-20 part chainextender and 80-99.9 part vector resin melting mixing be obtained.
Described chainextender, mainly for improving the melt strength of polyester, makes its suitable foaming.Utilize the reactive group in chainextender and the reactive group in polyester chain to carry out grafting, coupling or crosslinking reaction, improve melt strength, to meet cell stabilization.As chainextender, can use known, such as, many officials can roll into a ball oxazoline compound, polyfunctional isocyanate, multi-functional epoxy compound, multifunctional acid anhydrides etc.
Duo Guan Neng Tuan oxazoline compound can be aromatic substance also can be fatty compounds.It is such as ortho position, between position, or the sub-Ben Ji bisoxazoline of para-orientation, 2, two (2-oxazoline-2-base) pyridine (and oxazoline ring has the substituent derivative of alkyl or aryl) of 6-, 2, two (the 8H-indeno [1 of 6-, 2-d] oxazoline-2-base) pyridine, 1, 2-two (4, 4-dimethyl-2-oxazoline-2-base) ethane (and oxazoline ring has the substituent derivative of alkyl or aryl), 2, the segmented copolymer of the two-2-oxazoline (and oxazoline ring has the substituent derivative of alkyl or aryl) of 2-sec.-propyl and at least two Alpha-Methyl vinyl-2-oxazoline unit compositions, such as 1, 3-penylene-bis-(2-oxazoline), two (2-oxazoline), 1, 4-penylene-bisoxazoline, 2, 2-two (2-oxazoline) etc.
Polyfunctional isocyanate is aliphatic, alicyclic, aromatic vulcabond or polymeric polyisocyanate such as.Available containing the sub-amide group of carbonization two, carboxylamine base, allophanic acid base, cyamelide base, urea element base or the polymeric polyisocyanate of biuret groups, these can be described as " polymeric polyisocyanate of modification " or " isocyanate prepolymer ".Such as 1,8-diisocyanato-p-methane, diphenylmethanediisocyanate, cyclohexyl diisocyanate, phenylene diisocyanate, tolylene diisocyanate (comprise 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and crude tolylene diisocyanate), diphenylmethanediisocyanate, chlorophenylene diisocyanates, ditan-4,4 '-vulcabond is (also referred to as 4,4 '-diphenylmethanediisocyanate), naphthalene-1,5-vulcabond; Polymethylene multi-phenenyl isocyanate; Hexamethylene diisocyanate homopolymerization tripolymer, tolylene diisocyanate homopolymerization tripolymer, different Buddhist diisocyanates homopolymerization tripolymer, 4,4 '-ditan-vulcabond homopolymerization tripolymer, diphenylmethanediisocyanate homopolymerization tripolymer, 4,4-dicyclohexyl methane diisocyanate homopolymerization tripolymers, fourth vulcabond homopolymerization tripolymer, pungent vulcabond homopolymerization tripolymer, the last of the ten Heavenly stems vulcabond homopolymerization tripolymer and the homopolymerization tripolymer such as naphthalene diisocyanate homopolymerization tripolymer; Oneself two isocyanic acids, tolylene diisocyanate, different Buddhist diisocyanates, 4,4 '-ditan-vulcabond, tercopolyureas aggressiveness between diphenylmethanediisocyanate and 4,4-dicyclohexyl methane diisocyanate; Ethyl is seen sour vulcabond, C
2h
5p (O) (NCO)
2, phenyl sees sour vulcabond, C
6h
5p (O) (NCO)
2, containing the mixture of one or more arbitrary proportions of the compounds such as the compound of trivalent silicon cyanate group, the isocyanic ester that formed by sulphonamide, cyanic acid and thiocyanic acid.
Multi-functional epoxy compound refers to the compound in the molecule containing two or more epoxide groups.Comprise fatty compounds, such as polyoxyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane tris Synthesis of Oligo Ethylene Glycol etc.; Alicyclic compound, such as Hydrogenated Bisphenol A diglycidyl ether, hydrogenation diglycidyl isophthalic acid ester, methyl-3,4-epoxycyclohexane carboxylate, two (3,4-expoxycyclohexyl) adipic acid ester, four epoxy glycerite bis aminomethyl hexanaphthenes etc.; Heterogeneous ring compound, such as diglycidyl glycolylurea, diglycidyl base oxyalkyl glycolylurea, three epoxy glycerite isocyanic acid urea acid esters, three epoxy glycerite cyanates, three epoxy glycerite glycolylurea etc.; Aromatic substance, such as diglycidyl rthers of bisphenol-A, terephthalic acid diglycidyl ether initial condensates, ditan diglycidyl ether, terephthalic acid diepoxy glyceride, m-phthalic acid, the p-or m-amino-phenol of three Synthesis of Oligo Ethylene Glycol, four epoxy glycerite benzyl ethane, sorbyl alcohol four Synthesis of Oligo Ethylene Glycol, four epoxy glycerite tetramethyl triaminotriphenyl methane NH2s, cresol novolak epoxy resin etc.
In above-mentioned chainextender, to aspects such as the hazardness of human body and the accessibility of use, preferably polyfunctional epoxy compound and multifunctional acid anhydrides, particularly preferably is dicarboxylic anhydride.Preferred dicarboxylic anhydride is the dicarboxylic anhydride of following tetracarboxylic acid: 1, 2, 4, 5-pyromellitic acid, Pyromellitic Acid, 3, 3 ' 4, 4 '-benzophenone tetracarboxylic acid, 2, 2-two-(3, 4-dicarboxyphenyi)-propane, two-(3, 4-dicarboxyphenyi)-ether, two-(3, 4-dicarboxyphenyi)-thioether, two-(3, 4-dicarboxyphenyi)-sulfone, two-(3, 4-dicarboxyphenyi)-sulfoxide, naphthalene-2, 3, 6, 7-tetracarboxylic acid, tetrahydrofuran (THF)-2, 3, 4, 5-tetracarboxylic acid, 2, 2-two-(3, 4-dicarboxyphenyi) HFC-236fa, 1, 2, 5, 6-naphthalene tetracarboxylic acid and composition thereof.Particularly preferred dicarboxylic anhydride is pyromellitic acid anhydride.
Described vector resin is close with the processing temperature of phosphorous copolyester, and thermotolerance is high, at 300 DEG C, keep more than 10min not decompose, and has a resinoid of mobility.Such as, polyolefin resin, conjugated polyester resin, nylon resin or polycarbonate resin.Preferred PP resin, the one in polycarbonate and PETG resin.
Described whipping agent, can use known various whipping agents, such as chemical foaming agent and pneumatogen.Chemical foaming agent is mainly can the whipping agent of high temperature thermal decomposition, the such as thermal decomposition of blowing agent of various organic or inorganic.Organic blowing agent, such as nitroguanidine, oxalyl hydrazine, toluene yellow line Urea,amino-, 5-phenyltetrazole, carbonyl acid amides and di-isopropyl azodicarboxylate etc.; Inorganic foaming agent, such as barium azodicarboxylate, azo-2-carboxylic acid's strontium, aluminium hydroxide, magnesium hydroxide, supercarbonate and citric acid systems etc.Chemical foaming agent likely produces the small molecule by-product promoting flame-proof copolyester degraded in decomposition course, and the decomposition temperature of chemical foaming agent mate with the processing temperature of phosphorous copolyester require high, so preferred pneumatogen.Pneumatogen, comprises rare gas element, such as carbonic acid gas, nitrogen, argon gas and pressurized air etc.; Aliphatic hydrocarbon, such as propane, butane, pentane, Trimethylmethane, neopentane, iso-pentane, hexane and divinyl; Saturated alicyclic hydrocarbon, such as hexanaphthene; Tetrafluoroethane, hydrogenation fluorochlorohydrocarbon and (hydrogenation) fluothane hydrocarbon; Ether, such as methyl sec-butyl ether; Ketone, such as acetone.These can be used alone, also can arbitrary proportion used in combination.From the viewpoint of environmental protection, preferably use rare gas element, for the solubility coefficient of resin, more preferably carbonic acid gas and nitrogen.
Described nucleator can be talcum powder, calcium carbonate, calcium oxide, kaolin, barium sulfate, silicon-dioxide, aluminum oxide or aluminium hydroxide etc.
The present invention, by carrying out grafting, coupling or crosslinking reaction to the reactive group in the phosphorous copolyester chain in phosphorous copolyester premixed systems in extrusion, improves melt strength and the melt viscosity of phosphorous copolyester, thus forms stable foam structure.The density of the phosphorous copolyester foam that the present invention adopts phosphorous copolyester foam composition material to prepare is: 30-950kg/m
3.
The method of phosphorous copolyester foam prepared by employing phosphorous copolyester foam composition material of the present invention, it is characterized in that to be prepared by single stage method or these two kinds of methods of two-step approach.
Single stage method of the present invention, namely phosphorous copolyester adds foam extrusion machine together with tackifier, and modified foaming is moulding integrated, prepares phosphorous copolyester foam, it is characterized in that completing through the following steps:
100 parts of phosphorous copolyesters, 0.1-20 part tackifier, 0.1-20 part whipping agent and 0-10 part nucleator are mixed by forcing machine, modification under the melt temperature of phosphorous copolyester, by die extrusion foaming, obtain phosphorous copolyester foam, again by this foam traction, cutting, i.e. obtained finished product.
The feature of single stage method is that the thickening step that foams completes, and reduce equipment investment, production efficiency is high.Shortcoming is that chainextender usage quantity is large, and reaction not exclusively.Residual chainextender can reduce flameproof effect.
Two-step approach of the present invention, namely solid state reaction after blended granulation extruded by phosphorous copolyester and tackifier, preparation foaming level phosphorous copolyester, then carries out extrusion foaming, prepares phosphorous copolyester foam, it is characterized in that completing through the following steps:
1) by 100 parts of phosphorous copolyesters and the mixing of 0.1-20 part tackifier, reactive extrursion granulation under the melt temperature of phosphorous copolyester;
2) by step 1) in the particle made carry out high temperature solid-state reactions, this process completes the phosphorous copolyester of branching reaction preparation foaming level;
3) by step 2) phosphorous copolyester of the foaming level that obtains, 0.1-20 part whipping agent and 0-10 part nucleator be by forcing machine melting mixing, by die extrusion foaming, obtain phosphorous copolyester foam, then by this foam traction, cutting, i.e. obtained finished product.
The feature of two-step approach is that technique is long, but chainextender consumption is few, reacts completely.Foam article good flame retardation effect.
Phosphorous copolyester of the present invention, before mixing with tackifier, requires that moisture is at below 30ppm.Need at 160 DEG C at least dry 4h.
In content of the present invention, the step 2 in two-step approach) described in high temperature solid-state reactions, 120-230 DEG C can be heated to, holding temperature 1-30 hour under vacuum or rare gas element (as nitrogen, argon gas etc.) protection.
In content of the present invention, single stage method and the mouth mould described in two-step approach comprise rectangle die lip, annular port mould, T-shaped mouth mould, circular port mould, foraminous die plate (bar bubble boundling mouth mould) and other special-shaped mouth moulds etc.
In content of the present invention, single stage method and the extrusion equipment described in two-step approach, comprise single screw extrusion machine and tandem, twin screw extruder and tandem thereof, single twin screw extruder mixing tandem, smelt gear pump can be added between two forcing machines if desired.
As required, nucleator conventional in this area also can be added in content of the present invention, in two-step approach, nucleator is added in step (1), also can add in step (3), adding form can be directly add, and also can add with masterbatch (i.e. 0.1-20 part nucleator and 80-99.9 part vector resin melting mixing obtain the nucleator masterbatch) form known to art technology.Nucleator can be used to the heterogeneous nucleation impelling polyester of the present invention, adjustment cell density and abscess-size.
In addition, other additives also can with in the present invention, and these additives comprise: impact modifying agent, filler, stablizer, oxidation inhibitor, static inhibitor, tinting material, fuel and pigment.These additives, their consumption and their purposes are well-known in this technique.
The phosphorous copolyester foam adopting phosphorous copolyester foam composition material to prepare is being produced, and heating, shaping, sawing, trimming etc. can produce the scrap stock of some amount, not recycle and can cause the wasting of resources after processing further, and even environmental pollution, is necessary to be recycled to its melting.But phosphorous copolyester is after extrusion foaming, and its IV value can decline, directly may can not be used for extrusion foaming because melt strength is low, the mode of adding chainextender can be adopted to improve its melt strength and melt viscosity.In active reaction group in chainextender and scrap stock reactive group (as hydroxyl, carboxyl etc.) carry out grafting, coupling or crosslinking reaction, molecular chain is lengthened or produces side chain, improve molecular weight, thus improve melt strength and melt viscosity, to meet cell stabilization.So both can ensure the smooth of the phosphorous copolyester extrusion and foaming process that with the addition of scrap stock, also can ensure that the phosphorous copolyester foaming properties prepared met service requirements.These scrap stock add with the consumption of the 0.1%-50% relative to phosphorous copolyester weight.
The phosphorous copolyester foam that the present invention adopts phosphorous copolyester foam composition material to prepare has excellent fire resistance, can be used as the sandwich foam core material (as track traffic, vehicle, aviation, boats and ships, industry and furniture etc.) of high fire protection requirement and building structure and heat-insulation and heat-preservation bifunctional material, be with a wide range of applications.
Compared with prior art, the present invention has features and beneficial effect:
A phosphorous copolyester foam that () the present invention obtains has excellent fire resistance, and can meet the B level burning behavior class requirement of " material of construction and product burns grading performance " standard, and oxygen index is greater than 30%.
B phosphorous copolyester foam that () the present invention obtains can be used as the sandwich foam core material (as track traffic, aviation, boats and ships, industry and furniture etc.) of high fire protection requirement and building structure and heat-insulation and heat-preservation bifunctional material.
Embodiment
Below in conjunction with embodiment, the invention will be further elaborated.Embodiment only for being further described invention, instead of limits the present invention by any way, and the adjustment of nonessential improvement that the professional of the art makes according to above-mentioned content of the present invention, protection content of the present invention should be belonged to.
Embodiment is as follows for the material and testing method representing result:
Limiting viscosity (IV) Ubbelohde viscometer detects with 6: 4 mixed solvents of phenol and sym.-tetrachloroethane at 30 DEG C.
Phosphorus content testing method: choose the phosphorous copolyester section of more than 5 kinds different phosphate content as standard model, measure with ICP (jigger coupling high frequency plasma torch atomic emission spectrometry), according to the fluorescence intensity drawing standard curve of phosphorus content and correspondence.When testing the phosphorus content of foaming level phosphorous copolyester, according to the fluorescence intensity of the phosphoric of test, in typical curve, obtain corresponding phosphorus content.
Density detects according to ISO845.
Compression performance, according to ISO844-2007,100KN universal testing machine detects.
Cutting performance, according to ASTM C273,100KN universal testing machine detects.
Oxygen index, according to GB/T2406.1-2008, HC-2 type oxygen index measurer detects.
Embodiment and comparative example all prepare phosphorous copolyester foam on co-rotating twin screw extruder.This twin screw parameter is as follows: length-to-diameter ratio is 40: 1, and screw diameter is 49.2mm, and the mouth mould of foam shaping by extrusion is foraminous die plate (bar bubble boundling mouth mould).The parameter of foraminous die plate is as follows: 69 apertures of aperture 1.5mm line up rectangular uniform distribution with 6, and the distance of center circle in each hole is 7.5mm.
Embodiment 1 single stage method prepares phosphorous copolyester foam
Phosphorous copolyester (such as: the fire-retardant slice (phosphorous in main chain) of Jinan Hao Ersen company, IV value is 0.67dL/g, phosphorus content is 5600ppm), the drying 4 hours at 160 DEG C in dehumidifying heat pump respectively of tackifier (not containing vector resin) and nucleator.
100 weight part phosphorous copolyesters, 1.0 weight part tackifier (not containing vector resin), 2.0 parts by weight of blowing agent carbonic acid gas and 0.3 weight part talcum powder are mixed by twin screw extruder, reactive extrursion modification under the melt temperature of phosphorous copolyester, pass through foraminous die plate, through beaming device, the width obtaining merging is 10cm, thickness is 5cm, and density is 130kg/m
3phosphorous copolyester foam board.The rate of feeding of phosphorous copolyester is 20kg/h.The performance perameter of gained phosphorous copolyester foam is in table 1.
Forcing machine processing parameter is as follows:
Embodiment 2 two-step approach prepares phosphorous copolyester foam
Mixed with 90 parts of vector resin PP (such as: the T30s of Daqing petrochemical) by 10 parts of chainextenders, extruding pelletization under the melt temperature of PP, prepares tackifier;
Phosphorous copolyester (such as: the 8404-1G of Sichuan Dong Cai company, IV value is 1.05dL/g, and phosphorus content is 10000ppm), tackifier and nucleator in dehumidifying heat pump at 160 DEG C dry 6 hours respectively.
By 100 weight part phosphorous copolyesters, the reactive extrursion granulation at 265-270 DEG C of 3 weight part tackifier, after pre-crystallized drying, be placed in rotary drum tackifying equipment, solid state reaction 4h at 200 DEG C of temperature, preparation foaming level phosphorous copolyester.Dried foaming level phosphorous copolyester 100 weight part, 0.5 weight part talcum powder nucleator and 2.5 parts by weight of blowing agent carbonic acid gas are mixed by forcing machine, under the melt temperature of phosphorous copolyester, pass through foraminous die plate, through beaming device, the width obtaining merging is 10cm, thickness is 5cm, and density is 100kg/m
3phosphorous copolyester foam board.The rate of feeding of phosphorous copolyester is 20kg/h.The performance perameter of gained phosphorous copolyester foam is in table 1.
Embodiment 3
The present embodiment is as different from Example 2: phosphorous copolyester is the 8402-2 (phosphorous in main chain) of Sichuan Dong Cai company, and IV value is 0.645dL/g, and phosphorus content is 6780ppm.Other steps are with embodiment 2.
Mixed with 90 parts of vector resin PP (such as: the T30s of Daqing petrochemical) by 10 parts of chainextenders, extruding pelletization under the melt temperature of PP, prepares tackifier;
Phosphorous copolyester (such as: the 8402-2 (backbone chain type) of Sichuan Dong Cai company, IV value is 0.645dL/g), tackifier and nucleator calcium oxide in dehumidifying heat pump at 160 DEG C dry 6 hours respectively.
By 100 weight part phosphorous copolyesters, the reactive extrursion granulation at 265-270 DEG C of 3 weight part tackifier, after pre-crystallized drying, be placed in rotary drum tackifying equipment, solid state reaction 20h at 210 DEG C of temperature, foaming level phosphorous copolyester 100 weight part, 0.5 weight part calcium oxide nucleator and the 1.5 parts by weight of blowing agent carbonic acid gas of preparing foaming level phosphorous copolyester dried are mixed by forcing machine, under the melt temperature of phosphorous copolyester, pass through foraminous die plate, through beaming device, the width obtaining merging is 10cm, thickness is 5cm, and density is 150kg/m
3phosphorous copolyester foam board.The rate of feeding of phosphorous copolyester is 24kg/h.The performance perameter of gained phosphorous copolyester foam is in table 1.
Embodiment 4
The present embodiment is as different from Example 2: not containing vector resin in tackifier, namely adopts separately chainextender as tackifier.Other steps are with embodiment 2.
By 100 weight part phosphorous copolyesters (such as: the 8406-2 of Sichuan Dong Cai company, IV value is 0.64dL/g, phosphorus content is 12000ppm), 0.2 weight part tackifier (not containing vector resin) reactive extrursion granulation at 265-270 DEG C, after pre-crystallized drying, be placed in rotary drum tackifying equipment, 230 DEG C of temperature solid reaction 28h, preparation foaming level phosphorous copolyester.Dried foaming level phosphorous copolyester 100 weight part, 0.2 weight part nucleator calcium oxide, 10 parts by weight of blowing agent carbonic acid gas are mixed by forcing machine, modification under the melt temperature of phosphorous copolyester, pass through foraminous die plate, through beaming device, the width obtaining merging is 10cm, thickness is 5cm, and density is 80kg/m
3phosphorous copolyester foam board.The rate of feeding of phosphorous copolyester is 30kg/h.The performance perameter of gained phosphorous copolyester foam is in table 1.
Embodiment 5
The present embodiment is as different from Example 1: phosphorous copolyester is the fire-retardant slice ((phosphorous in main chain), its IV value is 0.675dL/g, and phosphorus content is 6882ppm) adopting Sichuan Fu Er new company.And use the tackifier containing vector resin.All the other steps are with embodiment 1.
By 20 parts of chainextenders, 80 parts of vector resin polycarbonate (such as: the L-1250Z of Di Ren company) mixing, extruding pelletization under the melt temperature of polycarbonate, prepares tackifier;
100 weight part phosphorous copolyesters, 10 weight part tackifier and 1 parts by weight of blowing agent nitrogen are mixed by twin screw extruder, reactive extrursion modification under the melt temperature of phosphorous copolyester, pass through foraminous die plate, through beaming device, the width obtaining merging is 10cm, thickness is 5cm, and density is 250-300kg/m
3phosphorous copolyester foam board.The rate of feeding of phosphorous copolyester is 20kg/h.The performance perameter of gained phosphorous copolyester foam is in table 1.
Embodiment 6
The present embodiment is as different from Example 2: phosphorous copolyester be phosphorous copolyester (such as: the 8406-2G of Sichuan Dong Cai company, IV value is 0.8dL/g, phosphorus content is 12000ppm) with conventional polyester (such as: the WB-8816 of China Resources, IV are 0.8dL/g) weight ratio be the mixture of 90: 10.Other steps are with embodiment 2.
Mixed with 99 parts of vector resin PP (such as: the T30s of Daqing petrochemical) by 1 part of chainextender, extruding pelletization under the melt temperature of PP, prepares tackifier;
Mixed with 99 parts of vector resin PP (such as: the T30s of Daqing petrochemical) by 1 part of nucleator talcum powder, extruding pelletization under the melt temperature of PP, prepares nucleator masterbatch;
By phosphorous copolyester, tackifier and nucleator in dehumidifying heat pump at 160 DEG C dry 6 hours respectively.
By 100 weight part phosphorous copolyesters, 20 weight part tackifier and the reactive extrursion granulation at 265-270 DEG C of 10 weight nucleator masterbatch, after pre-crystallized drying, be placed in rotary drum tackifying equipment, solid state reaction 8h at 170 DEG C of temperature, preparation foaming level phosphorous copolyester.Dried foaming level phosphorous copolyester 100 weight part and 0.5 parts by weight of blowing agent nitrogen are mixed by forcing machine, under the melt temperature of phosphorous copolyester, by foraminous die plate, through beaming device, the width obtaining merging is 10cm, thickness is 5cm, and density is 400kg/m
3phosphorous copolyester foam board.The rate of feeding of phosphorous copolyester is 40kg/h.The performance perameter of gained phosphorous copolyester foam is in table 1.
Comparative example 1
General common grade polyester chip (such as: the WB-8816 of China Resources, IV value is 0.8dL/g), the drying 6 hours at 160 DEG C in dehumidifying heat pump respectively of tackifier (not containing vector resin) and nucleator.
100 weight part general common level polyester, 0.5 weight part tackifier (not containing vector resin), 0.3 weight part nucleator and 2 parts by weight of blowing agent carbonic acid gas are mixed by twin screw extruder, modification under the melt temperature of general purpose grade polyester, pass through foraminous die plate, through beaming device, the width obtaining merging is 10cm, thickness is 5cm, and density is 120kg/m
3polyester form sheet material.The rate of feeding of general purpose grade polyester is 30kg/h.The performance perameter of gained polyester form is in table 1.
Table 1 embodiment and comparative example performance perameter table
Claims (13)
1. a phosphorous copolyester foam composition material, is characterized in that this premixed systems is prepared from by ratio of weight and the number of copies by following component:
100 portions of phosphorous copolyesters, 0.1-20 part tackifier, 0.1-20 part whipping agent and 0-10 part nucleators;
The phosphorus content of above-mentioned phosphorous copolyester is 10-20000ppm, IV value is 0.40-1.40dL/g;
Described phosphorous copolyester refers to:
The copolyesters obtained by response type P contained compound participation copolycondensation, comprises polyester phosphorous in polyester phosphorous in main chain and side chain; Or,
Be selected from random phosphorous copolyester, block phosphorous copolyester, grafting phosphorous copolyester or replace phosphorous copolyester; Or,
Be selected from the mixture of phosphorous PET copolyesters, phosphorous PBT copolyesters, phosphorous PTT copolyesters, phosphorous PEN copolyesters, phosphorous PCT copolyesters or their arbitrary proportions;
The density of described phosphorous copolyester foam is 30-950kg/m
3;
The tackifier that described tackifier are chainextender or 0.1-20 part chainextender and 80-99.9 part vector resin melting mixing are obtained, described chainextender is selected from many officials can roll into a ball oxazoline compound, polyfunctional isocyanate, multi-functional epoxy compound or multifunctional acid anhydrides;
Described whipping agent is selected from rare gas element, aliphatic hydrocarbon, saturated alicyclic hydrocarbon, fluothane hydrocarbon, ether, one or more arbitrary proportions of ketone used in combination.
2. phosphorous copolyester foam composition material as claimed in claim 1, it is characterized in that described phosphorous copolyester can be the blend of phosphorous copolyester and conventional polyester, in this blend, the weight content of phosphorous copolyester is 25% ~ 100%.
3. phosphorous copolyester foam composition material as claimed in claim 1 or 2, is characterized in that described phosphorous copolyester is phosphorous PET copolyesters.
4. the phosphorous copolyester foam composition material described in claim 1 or 2, is characterized in that the phosphorus content of phosphorous copolyester is 5000-18000ppm.
5. phosphorous copolyester foam composition material according to claim 2, is characterized in that described conventional polyester is the mixture of more than one arbitrary proportions of PET, PBT, PTT, PEN, PCT and their multipolymer or more polyester.
6. the phosphorous copolyester foam composition material described in claim 1 or 2, it is characterized in that described vector resin is close with the processing temperature of phosphorous copolyester, and thermotolerance is high, at 300 DEG C, keep more than 10min not decompose, there is the resin of mobility, be selected from polyolefin resin, conjugated polyester resin, nylon resin or polycarbonate resin.
7. phosphorous copolyester foam composition material according to claim 6, is characterized in that described vector resin is selected from PP resin, the one in polycarbonate and PETG resin.
8. the phosphorous copolyester foam composition material described in claim 1 or 2, is characterized in that described whipping agent is selected from carbonic acid gas in rare gas element or nitrogen.
9. the phosphorous copolyester foam composition material described in claim 1 or 2, is characterized in that described nucleator is selected from talcum powder, calcium carbonate, calcium oxide, kaolin, barium sulfate, silicon-dioxide, aluminum oxide or aluminium hydroxide.
10. adopting described in claim 1-9 any one adopts phosphorous copolyester foam composition material to prepare the method for phosphorous copolyester foam, it is characterized in that concrete steps are as follows: 100 parts of phosphorous copolyesters, 0.1-20 part tackifier, 0.1-20 part whipping agent and 0-10 part nucleator are passed through forcing machine blending and modifying under the melt temperature of phosphorous copolyester, by die extrusion foaming, obtain phosphorous copolyester foam, again by this foam traction, cutting, i.e. obtained finished product.
Adopt phosphorous copolyester foam composition material to prepare the method for phosphorous copolyester foam described in 11. employing claim 1-9 any one, it is characterized in that concrete steps are as follows:
1) by 100 parts of phosphorous copolyesters and the mixing of 0.1-20 part tackifier, reactive extrursion granulation under the melt temperature of phosphorous copolyester;
2) by step 1) in the particle made carry out high temperature solid-state reactions, this process completes the phosphorous copolyester of branching reaction preparation foaming level;
3) by 0-10 part step 2) phosphorous copolyester of the foaming level that obtains, 0.1-20 part whipping agent and 0-10 part nucleator be by forcing machine melting mixing, by die extrusion foaming, obtain phosphorous copolyester foam, then by this foam traction, cutting, i.e. obtained finished product.
12. methods as described in claim 10 or 11, is characterized in that described mouth mould comprises rectangle die lip, annular port mould, T-shaped mouth mould, circular port mould, foraminous die plate or other special-shaped mouth moulds.
13. methods as claimed in claim 11, it is characterized in that described solid state reaction is heated to 120-230 DEG C under vacuum or protection of inert gas, hold time 1-30 hour.
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| CN103360728A (en) | 2013-10-23 |
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