CN103360728A - 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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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 combination material and adopt this combination material to prepare the method for phosphorous copolyester foam, this phosphorous copolyester foam has good fire resistance, and can satisfy the B level burning behavior class requirement of " material of construction and goods classification system for fire performance " standard, oxygen index can be used as sandwich foam core material (such as track traffic, vehicle, aviation, boats and ships, industry and furniture etc.) and building structure and the heat-insulation and heat-preservation bifunctional material of high fire protection requirement greater than 30%.
Background technology
Polyester belongs to combustible material, its the time, the phenomenons such as heat release rate is large, calorific value is high, flame propagation speed, melting drippage, this characteristic makes its application at some key areas (such as track traffic, transportation, building, electron device, the vehicles, health care etc.) still be subject to certain restriction.
Since nineteen seventies, become increasingly active to fire-retardant research and the application and development of polyester in countries in the world, and the modification of flame retardant type polyester mainly is to take to add such as fire retardants such as halogen and phosphorus compounds therein.Existing studies show that contains halogen element, although particularly the fire retardant of chloride, bromine is comparatively effectively and be widely used, but the time easily discharge pungency and corrosive gas, such as hydrogen halide, dioxin etc., the people is sucked suffocate, thereby also be that the application of halogen containing flame-retardant is restricted; Existing studies show that, phosphorus are one of the most effective polyester flame-retardant element (Wang Yuzhong work, the design of fire-retardantization of trevira, Sichuan science and technology press, 1994).Phosphorus flame retardant pyrolysis when being heated is phosphoric acid, is converted at last poly-metaphosphoric acid or the tetra-sodium class product of vitreous state, forms sealing coat at material surface, stops heat transmission, reduces inflammable gas burst size and secluding air, reaches fire-retardant purpose.Certainly, fire retardation is difficult to realize 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, the adding mode by production process and fire retardant can be divided into following several mode:
(1) blending fire retardant modification: add fire retardant to the polyester system, do not change polyester production process;
(2) fire retardant is grafted polyester modified: make itself and reactive flame retardant generation Surface grafting reaction reach fire-retardant purpose at trevira or fabric;
(3) flame-retardant after-finishing: fabric is placed in the fire resistant fluid and floods the regular hour, takes out oven dry.
(4) conjugate spinning is flame-retardant modified: carry out conjugate spinning with conventional polyester and the polyester that contains flame-retardant composition.
(5) copolymerization is flame-retardant modified: carry out copolycondensation in esterification or polycondensation phase adding reactive flame retardant.
The 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 difficult for generally being adopted.Flame-retardant after-finishing, lack durability of fire-retardant, and feel, intensity, ventilation property and the color and luster of fabric etc. are produced larger impact, copolymerization is flame-retardant modified, because copolyreaction type phosphorus fire retardant has hydroxyl, two functional groups of carboxyl, 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 be the approval of present scientific circles and industry member from give in essence the polyester good flame-retardance can the flame retardant polyester technology.
Each company adopts the reactant of flame-retardant monomer, the different activities of different structure formula, different polymerizing condition and the difference of polymerization methods to prepare phosphorous copolyester, flame retardant effect also is 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:
A is the repeated structural unit of phosphor-containing flame-proof monomer in the formula, m and n are positive integer, and the intrinsic viscosity of this atactic polyester is 1.2-2.2dL/g, preferred 1.4-2.2dL/g, and 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.
The repeated structural unit A of phosphor-containing flame-proof monomer is at least a in the following structure in this atactic polyester:
In the formula, R
1For containing C
1-C
8Alkyl or phenyl or benzyl, R
2And R
3Be C
1-C
8Alkylidene group or aryl, the two can be identical can be not identical yet; X, Y and Z are the O atom.The limiting oxygen index(LOI) of this phosphorous atactic polyester can reach 33%, on the basis with excellent flame retardancy energy, has also improved its corresponding mechanical property, can be widely used in to make film, bottle class, protective clothing, tent, even the 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 also is a kind of in the 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, the 5-dihydroxy phenyl)-and the 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 it is contained, and to contain phosphorus component be at least a in the following phosphorous glycol:
Or the phosphorous diacid diol ester that makes through esterification for following phosphorous diacid and ethylene glycol or 1,3-PD or BDO is at least a:
Or be the mixture of any in any and the phosphorous diacid diol ester in the above-mentioned phosphorous glycol.The oxygen index of the fire-retardant blocked copolyester by method preparation can be up to 33%.
Chinese patent CN200810045357.6 discloses a kind of phosphoric flame-proof copolyester ionomer and preparation method thereof, and its used flame-retardant monomer is the compound with following general structure:
In the formula, R
1Be C
1-C
12Alkyl, aryl or benzyl; R
2Be C
1-C
8Alkylidene group or aryl; X is the O atom,
Perhaps for having 9 of a following general structure, the 10-dihydro-9-oxy is assorted-the 10-assorted luxuriant and rich with fragrance compounds of acyl of seeing:
In the formula, R
3Be propane-1，2，3-triyl, Y is the O atom, Z
1, Z
2Be hydroxy-acid group or ester group group, Z
1, Z
2Can be identical, can be not identical yet.
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, the fire-retardant rank of phosphorus series non-halogen flame retardant polyester polymeric articles that coupling by raw material and technique makes can reach the requirement of the high flame retardants such as 94UL V-0 level or VTM-0 level film, and limiting oxygen index(LOI) (LOI) is up to more than 45%.Can be used as the raw material that the production flame retardant properties reaches 94UL V-0 level or VTM-0 (being referred to as the V0 level) film, fire-retardant I level and above fire-retardant fibre and V0 level flame retardant plastics goods.Its described halogen-free phosphorus-containing copoly type fire retardant is the compound with following formula:
In the 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 phosphorus content in a kind of raising phosphorous copolyester of taking in order to make things convenient for blend processing phosphor-containing flame-proof polyester and goods thereof and has prepared manufacture method as the high-concentration phosphorus-contained copolyester of fire-retardant master granule.The molecular formula of its phosphorous organic reaction type fire retardant is:
In the 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 corresponding hydroxyalkyl; R
4: H, C
1-C
6Alkyl or corresponding hydroxyalkyl.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 the formula, R
1, R
2Be H atom or C
1-C
18Fisher's formula or cyclic alkyl, R
1, R
2Can be identical, can be not identical yet; R
3For functional group's group that can form ester group (has following structural formula :-COOR
5Or-OR
5, R wherein
5For the H atom or contain at least the C of a hydroxyl
1-C
12Alkyl); A
1Be 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 the formula, Ar
1Representing 3 valency aromatic groups, be the alkyl group of H atom or 1-20 carbon atom or aromatic alkyl group or the aralkoxy group of alkoxy grp or 6-20 carbon atom, for example 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:
R is alkyl group or phenyl, naphthyl and the xenyl group of 1-10 carbon atom in the formula; 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 the formula
1The alkyl group with hydroxyl for H atom or 1-10 carbon atom; R
2And R
3Alkyl group for halogen atom or 1-10 carbon atom; M and n represent the integer of 0-4.Concrete molecular formula can be following:
Also have at phosphorus flame retardant and introduce nitrogen element or phenyl raising flame retardant effect.Disclose a kind of nitrogenous phosphorus flame retardant such as Chinese patent CN200580014834.7, Chinese patent CN200410084108.X discloses a kind of response type phosphorus fire retardant that contains phenyl, and what use among the Chinese patent CN02109909.X also is to contain the phenyl phosphorus fire retardant.The preparation method with the flame-retarding phosphorus copolymerized polyester of good form and aspect that the PET hue that Chinese patent CN200810023617.X discloses a kind of production is good, flame retardant properties is excellent.The phosphorus flame retardant of its use is to have a kind of of following 3 kinds of general structures or more than one:
R wherein
1Be alkyl group or the alkoxy grp of nitrogen-containing group or 1-15 carbon atom, R
2Be the alkyl group of 1-9 carbon atom, R
3And R
4Alkyl group or the alkoxy grp of 1-15 carbon atom of expression, m and n represent the integer of 0-4, when m is the integer of 2-4, have a plurality of R
3Can be same to each other or different to each other; When n is the integer of 2-4, there is a plurality of R
4Can be same to each other or different to each other; A represents to contain the alkyl group that contains 3-6 carbon atom or the alkoxy grp of ester linkage.
In addition, US Patent No. 4587362, US4358045 and US4088205 have also used a class phosphonium flame retardant of Spirocyclic to prepare phosphorous copolyester, are mainly used in the fire-retardant of dacron fabric, and the structural formula of its fire retardant is as follows:
In sum, phosphorus be reactive flame retardant mainly contain phosphorus at main chain and phosphorus two kinds of forms on side chain, using at present more is the backbone chain type phosphorus fire retardant.Flame-proof copolyester can be random, block, grafting or flame-proof copolyester alternately.
The oxygen index of the phosphorous copolyester resin that above-mentioned patent system is standby is at least 25%, what have can be up to 45%, oxygen index about 21% much larger than conventional polyester, yet, obtained the vibrin of effective flameproof effect and limited range of application in the above patent, used such as aspects such as fiber, film, bottle class and Fire Retardant Industry silks.But these have the low extrusion foaming that can not directly should be used for of vibrin melt viscosities of flameproof effect, thereby these patents also have no requirement and cover the foam materials range of application.
Because the general purpose grade polyester, low such as the melt viscosity of terephthalic acid hexylene glycol ester (PET) and phosphorous copolyester, abscess easily breaks and can not become desirable foam materials when being used for extrusion foaming.Research is afterwards found by using suitable coupling agent can connect at the molecular chain of linearity side chain and then improving molecular weight and melt viscosity thereof.This development becomes possibility so that produce the thermoplastic polyester foam by extrusion and foaming process.The branching coupling agent is the chemical substance that contains a plurality of reactive functionality, can carry out condensation reaction and produce branched chain polymer with plural molecular chain.Melt extrude the branched chain polyester and suitable chemistry, physics or inert gas blown agent can be made the unicellular structure foam.
US Patent No. 522932 discloses a kind of method of polyester extrusion foaming, in polycondensation process, adds reactive functionality greater than 2 branching agent.The usage quantity of branching agent is in 1.5-6 equivalent concentration of per 100 mole of diacid.By polycondensation, the PET resin of branching is formed.Then use this branching resin 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 reclaim the PET resin of level, melt extrude give blend method at first with resin and the even mixing granulation of branching agent.Then solid particulate under vacuum or nitrogen protection, be heated to 170-220 ℃ then holding temperature finish 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 has reclaimed level PET resin melt blending in forcing machine, then in the method that directly adds the whipping agent extrusion foaming with the machine back segment.Can reduce the course of processing in this way, equipment investment and production time.But the reaction efficiency of branching agent does not have front two kinds of method height, and the content of residual branching agent is also higher in the froth product, and these residues seriously reduce the fire resistance of foam.In order to improve this technological process, US Patent No. 5696176 branching agent mother materials are developed.Mother material is to use polyethylene or polypropylene to make masterbatch as the branching agent blend of carrier and high density, then uses this masterbatch and general purpose grade or reclaims the common extrusion foaming of level PET resin.
Chinese patent CN200910302063.1 discloses a kind of method of utilizing the bottle level PET foaming to prepare the PET sheet material, its means by the acrylate multipolymer of interpolation polyfunctional group high reactivity material and nucleocapsid structure improve PET melt viscosity and intensity, add chemical foaming agent, preparation thickness is the PET sheet material of 0.8-1.5mm, and this PET sheet material is suitable for making food, medicine and electronic pallet etc.
Chinese patent CN99812803.1 discloses a kind of method of PET foam article, adopts the epoxy group(ing) coupling agent to improve the molecular weight of the polyester that has the PET type resin of lower molecular weight and fragility, particularly reclaims and improves its melt strength and swelling prepares.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 and add that the polyester raw material of whipping agent realizes by the extrusion molding intrinsic viscosity.This expanded polyester is for example for the manufacture of the plate, thin plate and the pipe that particularly use in building and encapsulation field.
Chinese patent CN 200980121758.8, a kind of pre-composition that adds thermoplastic elastomer and tetracarboxylic dianhydride in the vibrin is disclosed, and it is 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 that low-density core and the thin skin with high tensile are combined into one particular design body.This structure successfully is applied in requires lightweight, planar strength and the high industrial circle of rigidity, such as ships and light boats waterborne, aircraft, spacecraft, transportation and communication and other universal industrial fields.Sandwich structure composite material has specific function so to be because low-density core and the relative rigidity that has significantly improved the skin material after the skin material combines, and the weight increase of unit surface is very little.By selecting suitable skin material and the combination of core, 3% core that weight is skin material weight can improve respectively 7 times of 3.5 times of flexural strengths and bending stiffnesses.
The most frequent I-beam that sandwich structure composite material is likened to repetition of people.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 was subject to loading, power passed to another side from one side through core.The power that core is subjected to has pressure, draws and shearing force.The bending stiffness of sandwich structure composite material is directly proportional with the thickness of core, just as the rigidity of I-beam is directly proportional the same with distance between its upper and lower plates.When matrix material core thickness doubled, its flexural strength increased by six times, and bending stiffness increases twelvefold.
The over-all properties of core is extremely important in the core filled composite material.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 it is carried out lab investigation.These tests comprise compression, stretching and shearing test, and its performance index comprise intensity, modulus and anamorphic stretching rate etc.The most frequently used core has cork wood, honeycomb structure core, thermoplasticity and thermosetting foams core etc. in the industry of structure sandwich material.
Yet the made polyester form of above-mentioned patent process usually is unsuitable for doing sandwich material, because its foam aperture is too large, and pore size distribution is wide too, and this has caused poor mechanical property.In the foaming process that above-mentioned patent provides, the extrusion die that the polyester fondant that is mixed with the collateralization of volatile organic blowing agent or rare gas element is extruded through an annular or slit opening enters in the atmospheric environment.In atmospheric pressure state, whipping agent expansion polyester fondant and make it become foamy structure.As producing the thickness that reaches sandwich material requirement commonly used, then whipping agent makes the abscess-size of foamed products excessive overplumping, the problems such as the even irregular surface of skewness.
US Patent No. 7951449 discloses a kind of method for preparing the polyester form sandwich material of extruding, 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 on the template consistent those the bubble bars extruded by them of being arranged merge a mouthful mould boundling technology by the bar bubble uniform sequentially, can be the cystose without any space in conjunction with then melting closely.This piece patent makes PET become possibility as the sandwich structure material, and at first pushed market in 2005 by 3A company, Sweden DIAB, Switzerland GURIT and Belgian Armacell etc. are also released one after another separately PET foam core material and obtained corresponding market of important foam core material manufacturer of several families in the world, such as fields such as wind electricity blade and track traffics.
The polyester construction foam has the microvoid structure of trickle abscess, desirable dimensional stability, thermostability, chemical stability, good mechanical mechanics property, barrier property (heat-insulation and heat-preservation), antiultraviolet, water-absorbent is low, and its environmental friendliness, is easy to recycling.Just because of above-mentioned good characteristic, the 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 have obtained good application.But above-mentioned foam does not have, or only has lower fire resistance, does not basically reach the fire protection requirement of China's building industry.
The annual newly-increased floor area of building of China is about 2,000,000,000 square metres at present, and wherein the completed floor space of building curtain wall is 7,500 ten thousand square metres.Building curtain wall is the sandwich structure composite sheet substantially, and using the sandwich material area is 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 provide the wide market space for the New Building Materials development.Existing heat-insulating material mainly comprises: EPS, XPS, urethane, rock wool, glass wool, plank, foamed concrete etc.Can not reasonably unify at aspects such as environmental-protecting performance, mechanical property, processing characteristics, heat-insulating property, fire resistance, weather resistance and application properties, relative merits separately are obvious.Light foam lagging material does not wherein 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 day by day enhancing of environmental consciousness, the concept day of low-carbon emission reduction is advanced the popular feeling, requires New Building Materials 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 of several functions such as integrating fire prevention, antidetonation, insulation, waterproof, noise reduction, decoration with the structural foam sandwich material have become a kind of development trend.The energy saving building curtain wall of for example making with sandwich material can alleviate wall weight, improves the heat insulation effect of wall thermal insulating, and has good sound insulation, fire-retardant and erosion resistance.By adjusting structure, it also can be used as materials for wall, such as the body of wall in house inner wall and rapid-assembling room in addition, these rapid-assembling rooms can be used for disaster relief and rescue, the building site barracks also will be conducive to the builder and build faster common house, and this has subversive meaning at building materials field.
Market generally believes that the polyester construction foam core material can be used as the insulation type material of being combined with mechanical property at building field, can substitute above-mentioned existing high-strength, lightweight for building, heat insulation, fire-retardant material.The polyester construction foam core material uses as building, and precondition must satisfy the Building Fire Protection requirement.The polyester construction foam core material of commercially available stagnant combustion, low cigarette, just satisfied the requirement about fire resistance of the DIN5510 of field of track traffic, but its oxygen index only has about 26%, do not reach fire-retardant rank, be that oxygen index is not less than 28% requirement, just basically limited it and waited the application that high fire protection requirement field is arranged in building.
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, so that it can only be used at aspects such as fiber, film, bottle class and Fire Retardant Industry silk; (2) even present polyester form product adds fire retardant in preparation process, do not satisfy oxygen index yet and be not less than 28% application requiring.
Summary of the invention
For addressing the above problem, the applicant has carried out a large amount of further investigations to phosphorous copolyester, find that after deliberation the phosphorous copolyester that meets the following conditions simultaneously can be for the preparation of the 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 combination material, and adopt this combination material to prepare the method for phosphorous copolyester foam, this phosphorous copolyester foam has good fire resistance, and can satisfy the B level burning behavior class requirement of " material of construction and goods classification system for fire performance " standard, oxygen index can be used as sandwich foam core material (such as track traffic, vehicle, aviation, boats and ships, industry and furniture etc.) and building structure and the heat-insulation and heat-preservation bifunctional material of high fire protection requirement greater than 30.
Phosphorous copolyester foam combination material of the present invention is counted ratio by following components by weight parts and is prepared from: 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, preferred 5000-18000ppm; The IV value is 0.40-1.40dL/g.Foaming effect was bad when the IV value was lower than 0.40dL/g, and then cost is too high to be higher than 1.40dL/g.
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 above polyester).The weight content of phosphorous copolyester is 25%～100% in this blend.
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-hexanaphthene dimethyl ester) 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 participate in copolycondensation and the copolyesters that obtains by the response type P contained compound, and this phosphorous copolyester comprises polyester phosphorous in polyester phosphorous in the main chain and the side chain.For polyester phosphorous in the main chain, wherein the response type P contained compound is the compound with following general structure:
In the formula: R
1Be nitrogen-containing group or C
1-C
12Alkyl, aryl or benzyl; R
2Be H or C
1-C
6Alkyl or corresponding hydroxyalkyl; R
3Be C
1-C
8Alkylidene group or aryl; W is oh group, hydroxy-acid group or ester group group.For example:
Perhaps for having the compound of following general formula:
For example:
Perhaps for for example:
Deng the Spirocyclic P contained compound.
For polyester phosphorous in the side chain, wherein the response type P contained compound is to have 9 of a following general structure, the 10-dihydro-9-oxy is assorted-and the 10-assorted luxuriant and rich with fragrance compounds of acyl of seeing:
In the formula, R
4Be nitrogen-containing group or C
1-C
8Alkyl, aryl; R
5And R
6Be C
1-C
15Alkyl group or alkoxy grp; Y
1, Y
2Be H, hydroxy-acid group, hydroxyl or ester group group, Y
1, Y
2Can be identical, can be not identical yet, Y
1, Y
2Cannot be H simultaneously.M and n are the integer of 0-4.For example:
Phosphorous polyester in the preferred main chain of above-mentioned phosphorous copolyester.
Described tackifier can be chainextender or tackifier that 0.1-20 part chainextender and 80-99.9 part vector resin melting mixing are obtained.
Described chainextender, main in order to improve the melt strength of polyester, make its suitable foaming.Utilize reactive group and the reactive group in the polyester chain in the chainextender to carry out grafting, coupling or crosslinking reaction, improve melt strength, to satisfy cell stabilization.As chainextender, can use knownly, for example, 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 that aromatic substance also can be fatty compounds.It for example is the ortho position, between the position, or the inferior Ben Ji bisoxazoline of para-orientation, 2, two (2-oxazoline-2-yl) pyridines (and Zai oxazoline ring has the substituent derivative of alkyl or aryl) of 6-, 2, two (the 8H-indenos [1 of 6-, 2-d] oxazoline-2-yl) pyridine, 1,2-two (4,4-dimethyl-2-oxazoline-2-yl) ethane (and Zai oxazoline ring has the substituent derivative of alkyl or aryl), 2, the 2-sec.-propyl is two-2-oxazoline (and Zai oxazoline ring has the substituent derivative of alkyl or aryl) and at least two segmented copolymers that Alpha-Methyl vinyl-2-oxazoline unit forms, for example 1,3-penylene-two (2-oxazoline), two (2-oxazolines), 1,4-penylene-bisoxazolines, 2,2-two (2-oxazoline) etc.
The polyfunctional isocyanate is aliphatic, alicyclic, aromatic vulcabond or polymeric polyisocyanate for example.The available polymeric polyisocyanate that contains carbonization two inferior amide group, carboxylamine base, allophanic acid base, cyamelide base, urea element base or biuret groups, these can be described as " polymeric polyisocyanate of modification " or " isocyanate prepolymer ".For example 1,8-is diisocyanate based-and p-methane, diphenylmethanediisocyanate, cyclohexyl diisocyanate, phenylene diisocyanate, tolylene diisocyanate (comprises 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and rough tolylene diisocyanate), diphenylmethanediisocyanate, chlorinated benzene vulcabond, ditan-4,4 '-vulcabond (is also referred to as 4,4 '-diphenylmethanediisocyanate), naphthalene-1, the 5-vulcabond; Polymethylene multi-phenenyl isocyanate; Hexamethylene diisocyanate homopolymerization tripolymer, tolylene diisocyanate homopolymerization tripolymer, different Buddhist diketone vulcabond homopolymerization tripolymer, 4,4 '-ditan-vulcabond homopolymerization tripolymer, diphenylmethanediisocyanate homopolymerization tripolymer, 4,4-dicyclohexyl methane diisocyanate homopolymerization tripolymer, fourth vulcabond homopolymerization tripolymer, hot vulcabond homopolymerization tripolymer, the last of the ten Heavenly stems homopolymerization tripolymer such as vulcabond homopolymerization tripolymer and naphthalene diisocyanate homopolymerization tripolymer; Oneself two isocyanic acids, tolylene diisocyanate, different Buddhist diketone vulcabond, 4, the tercopolyureas aggressiveness between 4 '-ditan-vulcabond, diphenylmethanediisocyanate and 4, the 4-dicyclohexyl methane diisocyanate; Ethyl see sour vulcabond, C
2H
5P (O) (NCO)
2, phenyl see sour vulcabond, C
6H
5P (O) (NCO)
2, contain the compound of trivalent silicon cyanate group, the mixture of one or more arbitrary proportions of the compounds such as isocyanic ester that formed by sulphonamide, cyanic acid and thiocyanic acid.
The multi-functional epoxy compound refers to contain the compound of two or more epoxide groups in molecule.Comprise fatty compounds, for example 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, for example Hydrogenated Bisphenol A diglycidyl ether, hydrogenation diepoxy glycerine isophthalic acid ester, methyl-3,4-epoxy-cyclohexane carboxylicesters, two (3,4-epoxy group(ing) cyclohexyl) adipic acid ester, Fourth Ring oxygen glycerine diamino methylcyclohexane etc.; Heterogeneous ring compound, such as diepoxy glycerine glycolylurea, diepoxy glyceryl 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, the initial condenses of terephthalic acid diglycidyl ether, ditan diglycidyl ether, terephthalic acid diepoxy glyceride, m-phthalic acid, the p-or meta-amino-phenol of three Synthesis of Oligo Ethylene Glycol, Fourth Ring oxygen glycerine benzyl ethane, sorbyl alcohol Fourth Ring oxygen glyceryl ether, Fourth Ring oxygen glycerine tetramethyl triaminotriphenyl methane NH2, cresols-linear phenolic epoxy resin etc.
In above-mentioned chainextender, to the hazardness of human body and the aspects such as accessibility of use, preferably polyfunctional epoxy compound and multifunctional acid anhydrides particularly preferably are 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-pair-(3,4-dicarboxyl phenyl)-propane, two-(3,4-dicarboxyl phenyl)-and ether, two-(3,4-dicarboxyl phenyl)-thioether, two-(3,4-dicarboxyl phenyl)-and sulfone, two-(3,4-dicarboxyl phenyl)-sulfoxide, naphthalene-2,3,6, the 7-tetracarboxylic acid, tetrahydrofuran (THF)-2,3,4,5-tetracarboxylic acid, 2,2-pair-(3,4-dicarboxyl phenyl) 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, does not decompose more than the 10min 300 ℃ of lower maintenances, has a resinoid of flowability.For example, polyolefin resin, conjugated polyester resin, nylon resin or polycarbonate resin.Preferred PP resin, a kind of in polycarbonate and the PETG resin.
Described whipping agent can use known various whipping agents, for example chemical foaming agent and pneumatogen.But chemical foaming agent is mainly the whipping agent of high temperature thermolysis, for example the thermal decomposition of blowing agent of various organic or inorganics.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 system etc.Chemical foaming agent might produce the small molecule by-product that promotes the flame-proof copolyester degraded in decomposition course, and the requirement of the processing temperature of the decomposition temperature of chemical foaming agent and phosphorous copolyester coupling is high, so preferred pneumatogen.Pneumatogen comprises rare gas element, such as carbonic acid gas, nitrogen, argon gas and pressurized air etc.; Aliphatic hydrocarbon, for example propane, butane, pentane, Trimethylmethane, neopentane, iso-pentane, hexane and divinyl; Saturated alicyclic hydrocarbon, for example hexanaphthene; Tetrafluoroethane, hydrogenation fluorochlorohydrocarbon and (hydrogenation) fluothane hydrocarbon; Ether, for example methyl sec-butyl ether; Ketone, for example acetone.These can use separately, also can mix use by arbitrary proportion.Consider from the environmental protection aspect, 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 improves melt strength and the melt viscosity of phosphorous copolyester, thereby forms stable foam structure by in extrusion the reactive group in the phosphorous copolyester chain in the phosphorous copolyester combination material being carried out grafting, coupling or crosslinking reaction.The present invention adopts the density of the phosphorous copolyester foam of phosphorous copolyester foam combination material preparation to be: 30-950kg/m
3
Employing phosphorous copolyester foam combination material of the present invention prepares the method for phosphorous copolyester foam, and it is characterized in that can be by single stage method or these two kinds of method preparations of two-step approach.
Single stage method of the present invention, namely phosphorous copolyester and tackifier add foam extrusion machine together, and modified foaming is moulding integrated, and preparation phosphorous copolyester foam is characterized in that and can finish 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 the die extrusion foaming, obtain the phosphorous copolyester foam, with this foam traction, cutting, namely make finished product again.
The characteristics of single stage method are to finish in one step of tackify foaming, reduce equipment investment, and production efficiency is high.Shortcoming is that the chainextender usage quantity is large, and reaction not exclusively.Residual chainextender can reduce flameproof effect.
Two-step approach of the present invention, namely phosphorous copolyester and tackifier are extruded solid state reaction after the blend granulation, and a preparation foaming level phosphorous copolyester carries out extrusion foaming again, and preparation phosphorous copolyester foam is characterized in that and can finish through the following steps:
1) 100 parts of phosphorous copolyesters and 0.1-20 part tackifier are mixed, under the melt temperature of phosphorous copolyester, react extruding pelletization;
2) with step 1) in the particle made carry out high temperature solid-state reactions, this process is finished the phosphorous copolyester of branching reaction preparation foaming level;
3) with step 2) phosphorous copolyester, 0.1-20 part whipping agent and 0-10 part nucleator of the foaming level that obtains be by the forcing machine melting mixing, by the die extrusion foaming, obtain the phosphorous copolyester foam, with this foam traction, cutting, namely make finished product again.
The characteristics of two-step approach are that technique is long, but the chainextender consumption is few, reacts completely.The foam article good flame retardation effect.
Phosphorous copolyester of the present invention with before tackifier mix, requires moisture below 30ppm.Need dry at least 4h under 160 ℃.
In the content of the present invention, the step 2 in the two-step approach) high temperature solid-state reactions described in, can vacuum or rare gas element (such as nitrogen, argon gas etc.) protection under be heated to 120-230 ℃, holding temperature 1-30 hour.
In the content of the present invention, the mouth mould described in single stage method and the two-step approach comprises rectangle die lip, annular port mould, T-shaped mouthful of mould, circular port mould, foraminous die plate (bar bubble boundling mouth mould) and other abnormity mouthful moulds etc.
In the content of the present invention, extrusion equipment described in single stage method and the two-step approach, comprise that single screw extrusion machine and tandem thereof, twin screw extruder and tandem thereof, single twin screw extruder mix tandem, can add smelt gear pump in case of necessity between two forcing machines.
As required, also can add nucleator commonly used in this area in the content of the present invention, nucleator is added in the step (1) in the two-step approach, also can in step (3), add, the adding form can be direct adding, also can add with the masterbatch known to the art technology (being the nucleator masterbatch that 0.1-20 part nucleator and 80-99.9 part vector resin melting mixing obtain) form.Nucleator can be used to impel the heterogeneous nucleation of polyester of the present invention, adjusts cell density and abscess-size.
In addition, other additives also can be 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 present technique.
Adopt the phosphorous copolyester foam of phosphorous copolyester foam combination material preparation producing, and heating, moulding, after sawing, trimming etc. are further processed, can produce the scrap stock of some amount, not recycle and to cause the wasting of resources, and even environmental pollution is necessary its melting is recycled.Yet phosphorous copolyester is behind extrusion foaming, and its IV value can descend, and may can not directly be used for because melt strength is low extrusion foaming, can adopt the mode of adding chainextender to improve its melt strength and melt viscosity.In active reaction group in the chainextender and the scrap stock reactive group (such as hydroxyl, carboxyl etc.) carry out grafting, coupling or crosslinking reaction, molecular chain is lengthened or the generation side chain, improved molecular weight, thereby improved melt strength and melt viscosity, to satisfy cell stabilization.So both can guarantee to have added scrap stock the phosphorous copolyester extrusion and foaming process smoothly, can guarantee that also the phosphorous copolyester foaming properties for preparing satisfies service requirements.These scrap stock add with the consumption with respect to the 0.1%-50% of phosphorous copolyester weight.
The present invention adopts the phosphorous copolyester foam of phosphorous copolyester foam combination material preparation to have good fire resistance, can be used as sandwich foam core material (such as track traffic, vehicle, aviation, boats and ships, industry and furniture etc.) and building structure and the heat-insulation and heat-preservation bifunctional material of high fire protection requirement, be with a wide range of applications.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(a) the phosphorous copolyester foam that makes of the present invention has good fire resistance, and can satisfy the B level burning behavior class requirement of " material of construction and goods classification system for fire performance " standard, and oxygen index is greater than 30%.
(b) the phosphorous copolyester foam that makes of the present invention can be used as sandwich foam core material (such as track traffic, aviation, boats and ships, industry and furniture etc.) and building structure and the heat-insulation and heat-preservation bifunctional material of high fire protection requirement.
Embodiment
The invention will be further elaborated below in conjunction with embodiment.Embodiment only is used for invention is further described, rather than limits the present invention by any way, and the nonessential improved adjustment made according to above-mentioned content of the present invention of the professional of the art, should belong to protection content of the present invention.
Material and testing method that embodiment is used for the expression result are as follows:
Limiting viscosity (IV) detects at 30 ℃ of lower 6: 4 mixed solvents with phenol and sym.-tetrachloroethane with Ubbelohde viscometer.
Phosphorus content testing method: choose the phosphorous copolyester section of different phosphate content more than 5 kinds as standard model, measure with ICP (jigger coupling high frequency plasma torch atomic emission spectrometry), according to phosphorus content and corresponding fluorescence intensity drawing standard curve.When testing the phosphorus content of foaming level phosphorous copolyester, according to the fluorescence intensity of the phosphoric of testing, in typical curve, obtain corresponding phosphorus content.
Density detects according to ISO845.
Compression performance detects at the 100KN universal testing machine according to ISO844-2007.
Cutting performance detects at the 100KN universal testing machine according to ASTM C273.
Oxygen index detects at HC-2 type oxygen index measurer according to GB/T2406.1-2008.
Embodiment and comparative example are all at co-rotating twin screw extruder preparation phosphorous copolyester foam.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 are lined up rectangular uniform with 6 and are distributed, and the distance of center circle in each hole is 7.5mm.
Embodiment 1 single stage method prepares the phosphorous copolyester foam
Phosphorous copolyester (for example: Jinan person of outstanding talent and the fire-retardant slice (phosphorous in the main chain) of gloomy company, the IV value is 0.67dL/g, phosphorus content is 5600ppm), tackifier (not containing vector resin) and nucleator respectively in dehumidifying heat pump 160 ℃ lower dry 4 hours.
100 weight part phosphorous copolyesters, 1.0 weight part tackifier (not containing vector resin), 2.0 weight part whipping agent carbonic acid gas and 0.3 weight part talcum powder are mixed by twin screw extruder, modification is extruded in reaction under the melt temperature of phosphorous copolyester, pass through foraminous die plate, through beaming device, the width that obtains merging is that 10cm, thickness are 5cm, and density is 130kg/m
3The phosphorous copolyester foam board.The rate of feeding of phosphorous copolyester is 20kg/h.The performance perameter of gained phosphorous copolyester foam sees Table 1.
The forcing machine processing parameter is as follows:
Embodiment 2 two-step approachs prepare the phosphorous copolyester foam
(for example: the T30s of Daqing petrochemical) mix, extruding pelletization under the melt temperature of PP prepares tackifier with 90 parts of vector resin PP with 10 parts of chainextenders;
Phosphorous copolyester (for example: the 8404-1G of Sichuan east material company, IV value be 1.05dL/g, phosphorus content is 10000ppm), tackifier and nucleator be 160 ℃ times dryings 6 hours in dehumidifying heat pump respectively.
100 weight part phosphorous copolyesters, 3 weight part tackifier in 265-270 ℃ of lower reaction extruding pelletization, after the pre-crystallized drying, are placed the rotary drum tackifying equipment, solid state reaction 4h under 200 ℃ of temperature, preparation foaming level phosphorous copolyester.Dry good foaming level phosphorous copolyester 100 weight parts, 0.5 weight part talcum powder nucleator and 2.5 weight part whipping agent carbonic acid gas mix by forcing machine, under the melt temperature of phosphorous copolyester, pass through foraminous die plate, through beaming device, the width that obtains merging is that 10cm, thickness are 5cm, and density is 100kg/m
3The phosphorous copolyester foam board.The rate of feeding of phosphorous copolyester is 20kg/h.The performance perameter of gained phosphorous copolyester foam sees Table 1.
Embodiment 3
Present embodiment is as different from Example 2: phosphorous copolyester is the 8402-2 (phosphorous in the main chain) of east, Sichuan material company, and the IV value is 0.645dL/g, and phosphorus content is 6780ppm.Other steps are with embodiment 2.
(for example: the T30s of Daqing petrochemical) mix, extruding pelletization under the melt temperature of PP prepares tackifier with 90 parts of vector resin PP with 10 parts of chainextenders;
Phosphorous copolyester (for example: the 8402-2 (backbone chain type) of Sichuan east material company, IV value be 0.645dL/g), tackifier and nucleator calcium oxide be 160 ℃ times dryings 6 hours in dehumidifying heat pump respectively.
With 100 weight part phosphorous copolyesters, 3 weight part tackifier reaction extruding pelletization under 265-270 ℃, after the pre-crystallized drying, place the rotary drum tackifying equipment, solid state reaction 20h under 210 ℃ of temperature, dry good foaming level phosphorous copolyester 100 weight parts, 0.5 weight part calcium oxide nucleator and the 1.5 weight part whipping agent carbonic acid gas of preparation foaming level phosphorous copolyester mix by forcing machine, under the melt temperature of phosphorous copolyester, pass through foraminous die plate, through beaming device, the width that obtains merging is that 10cm, thickness are 5cm, and density is 150kg/m
3The phosphorous copolyester foam board.The rate of feeding of phosphorous copolyester is 24kg/h.The performance perameter of gained phosphorous copolyester foam sees Table 1.
Embodiment 4
Present embodiment is as different from Example 2: do not contain vector resin in the tackifier, namely adopt separately chainextender as tackifier.Other steps are with embodiment 2.
With 100 weight part phosphorous copolyesters (for example: the 8406-2 of east, Sichuan material company, the IV value is 0.64dL/g, phosphorus content is 12000ppm), 0.2 weight part tackifier (not containing vector resin) are in 265-270 ℃ of lower reaction extruding pelletization, after the pre-crystallized drying, place the rotary drum tackifying equipment, 230 ℃ of temperature solid state reaction 28h, preparation foaming level phosphorous copolyester.Dry good foaming level phosphorous copolyester 100 weight parts, 0.2 weight part nucleator calcium oxide, 10 weight part whipping agent carbonic acid gas mix by forcing machine, modification under the melt temperature of phosphorous copolyester, pass through foraminous die plate, through beaming device, the width that obtains merging is that 10cm, thickness are 5cm, and density is 80kg/m
3The phosphorous copolyester foam board.The rate of feeding of phosphorous copolyester is 30kg/h.The performance perameter of gained phosphorous copolyester foam sees Table 1.
Embodiment 5
Present embodiment is as different from Example 1: phosphorous copolyester is the fire-retardant slice that adopts Sichuan Fu Er new company ((phosphorous in the main chain), its IV value is 0.675dL/g, phosphorus content is 6882ppm).And use the tackifier that contain vector resin.All the other steps are with embodiment 1.
With 20 parts of chainextenders, 80 parts of vector resin polycarbonate (for example: the L-1250Z of Supreme Being people company) mix extruding pelletization under the melt temperature of polycarbonate, preparation tackifier;
100 weight part phosphorous copolyesters, 10 weight part tackifier and 1 weight part whipping agent nitrogen are mixed by twin screw extruder, modification is extruded in reaction under the melt temperature of phosphorous copolyester, pass through foraminous die plate, through beaming device, the width that obtains merging is that 10cm, thickness are 5cm, and density is 250-300kg/m
3The phosphorous copolyester foam board.The rate of feeding of phosphorous copolyester is 20kg/h.The performance perameter of gained phosphorous copolyester foam sees Table 1.
Embodiment 6
Present embodiment is as different from Example 2: phosphorous copolyester be phosphorous copolyester (for example: the 8406-2G of east, Sichuan material company, the IV value is 0.8dL/g, phosphorus content is 12000ppm) with conventional polyester (for example: the WB-8816 of China Resources, IV are 0.8dL/g) weight ratio be 90: 10 mixture.Other steps are with embodiment 2.
(for example: the T30s of Daqing petrochemical) mix, extruding pelletization under the melt temperature of PP prepares tackifier with 99 parts of vector resin PP with 1 part of chainextender;
(for example: the T30s of Daqing petrochemical) mix, extruding pelletization under the melt temperature of PP prepares nucleator masterbatch with 99 parts of vector resin PP with 1 part of nucleator talcum powder;
With phosphorous copolyester, tackifier and nucleator respectively in dehumidifying heat pump 160 ℃ lower dry 6 hours.
100 weight part phosphorous copolyesters, 20 weight part tackifier and 10 weight nucleator masterbatch in 265-270 ℃ of lower reaction extruding pelletization, after the pre-crystallized drying, are placed the rotary drum tackifying equipment, solid state reaction 8h under 170 ℃ of temperature, preparation foaming level phosphorous copolyester.Dry good foaming level phosphorous copolyester 100 weight parts and 0.5 weight part whipping agent nitrogen mixes by forcing machine, under the melt temperature of phosphorous copolyester, by foraminous die plate, through beaming device, the width that obtains merging is that 10cm, thickness are 5cm, and density is 400kg/m
3The phosphorous copolyester foam board.The rate of feeding of phosphorous copolyester is 40kg/h.The performance perameter of gained phosphorous copolyester foam sees Table 1.
Comparative example 1
General common grade polyester chip (for example: the WB-8816 of China Resources, the IV value is 0.8dL/g), tackifier (not containing vector resin) and nucleator respectively in dehumidifying heat pump 160 ℃ lower dry 6 hours.
100 weight part general common level polyester, 0.5 weight part tackifier (not containing vector resin), 0.3 weight part nucleator and 2 weight part whipping 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 that obtains merging is that 10cm, thickness are 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 sees Table 1.
Table 1 embodiment and comparative example performance perameter table
Claims (20)
1. a phosphorous copolyester foam combination is expected, it is characterized in that this combination material is to be 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 that 10-20000ppm, IV value are 0.40-1.40dL/g.
2. phosphorous copolyester foam combination material as claimed in claim 1 or 2 is characterized in that described phosphorous copolyester can be the blend of phosphorous copolyester and conventional polyester.The weight content of phosphorous copolyester is 25%～100% in this blend.
3. phosphorous copolyester foam combination as claimed in claim 1 or 2 is expected, it is characterized in that described phosphorous copolyester refers to the copolyesters that is obtained by response type P contained compound participation copolycondensation, comprises polyester phosphorous in polyester phosphorous in the main chain and the side chain.
4. claim 1 or 2 described phosphorous copolyester foam combination material is characterized in that described phosphorous copolyester is selected from random altogether phosphorous copolyester, block phosphorous copolyester, grafting phosphorous copolyester or replaces phosphorous copolyester.
5. claim 1 or 2 described phosphorous copolyester foam combination material is characterized in that described phosphorous copolyester is selected from the mixture of phosphorous PET copolyesters, phosphorous PBT copolyesters, phosphorous PTT copolyesters, phosphorous PEN copolyesters, phosphorous PCT copolyesters or their arbitrary proportions.
6. phosphorous copolyester foam combination material as claimed in claim 5 is characterized in that described phosphorous copolyester is phosphorous PET copolyesters.
7. claim 1 or 2 described phosphorous copolyester foam combinations expect that the phosphorus content that it is characterized in that phosphorous copolyester is 5000-18000ppm.
8. phosphorous copolyester foam combination material claimed in claim 2 is characterized in that described conventional polyester is the mixture of PET, PBT, PTT, PEN, PCT and their multipolymer or above more than one arbitrary proportions of polyester.
9. claim 1 or 2 described phosphorous copolyester foam combinations expect that the density that it is characterized in that described phosphorous copolyester foam is 30-950kg/m
3
10. claim 1 or 2 described phosphorous copolyester foams combination material is characterized in that described tackifier are chainextender or tackifier that 0.1-20 part chainextender and 80-99.9 part vector resin melting mixing are obtained.
11. phosphorous copolyester foam combination material claimed in claim 10 is characterized in that described chainextender is selected from many officials and can rolls into a ball oxazoline compound, polyfunctional isocyanate, multi-functional epoxy compound or multifunctional acid anhydrides.
12. phosphorous copolyester foam combination material claimed in claim 10, it is characterized in that described vector resin is close with the processing temperature of phosphorous copolyester, and thermotolerance is high, do not decompose more than the 10min 300 ℃ of lower maintenances, has mobile resin, be selected from polyolefin resin, conjugated polyester resin, nylon resin or polycarbonate resin.
13. the described phosphorous copolyester foam of claim 12 combination material is characterized in that described vector resin is selected from the PP resin, a kind of in polycarbonate and the PETG resin.
14. claim 1 or 2 described phosphorous copolyester foam combination material is characterized in that described whipping agent is selected from rare gas element, aliphatic hydrocarbon, and saturated alicyclic hydrocarbon, the fluothane hydrocarbon, ether, the mixing of one or more arbitrary proportions of ketone is used.
15. the described phosphorous copolyester foam combination of claim 13 material is characterized in that described whipping agent is selected from carbonic acid gas or the nitrogen in the rare gas element.
16. claim 1 or 2 described phosphorous copolyester foam combination material 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.
17. adopt the described employing phosphorous copolyester of claim 1-16 any one foam combination 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 the forcing machine blending and modifying under the melt temperature of phosphorous copolyester, by the die extrusion foaming, obtain the phosphorous copolyester foam, with this foam traction, cutting, namely make finished product again.
18. adopt the described employing phosphorous copolyester of claim 1-16 any one foam combination material to prepare the method for phosphorous copolyester foam, it is characterized in that concrete steps are as follows:
1) 100 parts of phosphorous copolyesters and 0.1-20 part tackifier are mixed, under the melt temperature of phosphorous copolyester, react extruding pelletization;
2) with step 1) in the particle made carry out high temperature solid-state reactions, this process is finished the phosphorous copolyester of branching reaction preparation foaming level;
3) with 0-10 part step 2) phosphorous copolyester, 0.1-20 part whipping agent and 0-10 part nucleator of the foaming level that obtains be by the forcing machine melting mixing, by the die extrusion foaming, obtain the phosphorous copolyester foam, with this foam traction, cutting, namely make finished product again.
19. such as claim 17 or 18 described methods, it is characterized in that described mouthful of mould comprises rectangle die lip, annular port mould, T-shaped mouthful of mould, circular port mould, foraminous die plate or other abnormity mouthful moulds.
20. method as claimed in claim 18 is characterized in that described solid state reaction is to be heated to 120-230 ℃ under vacuum or protection of inert gas, holds time 1-30 hour.
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| CN115109396A (en) * | 2022-07-21 | 2022-09-27 | 北京化工大学 | Halogen-free flame-retardant PET (polyethylene terephthalate) blended foaming material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006118008A1 (en) * | 2005-04-28 | 2006-11-09 | Kaneka Corporation | Flame-retardant low-resilience urethane foam cushion |
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2012
- 2012-03-26 CN CN201210083654.6A patent/CN103360728B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006118008A1 (en) * | 2005-04-28 | 2006-11-09 | Kaneka Corporation | Flame-retardant low-resilience urethane foam cushion |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115109396A (en) * | 2022-07-21 | 2022-09-27 | 北京化工大学 | Halogen-free flame-retardant PET (polyethylene terephthalate) blended foaming material and preparation method thereof |
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| CN103360728B (en) | 2015-07-15 |
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