CN105694386A

CN105694386A - Composition for preparation of phosphorus-containing copolyester foam and method for preparing phosphorus-containing copolyester foam from composition

Info

Publication number: CN105694386A
Application number: CN201610134890.4A
Authority: CN
Inventors: 马文光; 李巍; 丁盛; 顾唯开; 徐强; 于民栋
Original assignee: CHANGZHOU TIANSHENG NEO-MATERIAL Co Ltd
Current assignee: CHANGZHOU TIANSHENG NEO-MATERIAL Co Ltd
Priority date: 2016-03-09
Filing date: 2016-03-09
Publication date: 2016-06-22

Abstract

The invention belongs to the technical field of new materials and particularly relates to composition for preparation of phosphorus-containing copolyester foam and a method for preparing phosphorus-containing copolyester foam from the composition. The phosphorus-containing copolyester composition comprises the following components in parts by weight: 100 parts of universal polyester, 0.1-30 parts of a reactive phosphorus-containing flame retardant, 0.1-15 parts of a tackifier, 0.1-15 parts of a foaming agent and 0-8 parts of a nucleating agent. The content of phosphorus in the phosphorus-containing foamed copolyester composition is 5,000-20,000ppm, and the IV value is 1.10-1.40 dL/g. According to the phosphorus-containing foamed copolyester composition and the method for preparing the phosphorus-containing copolyester foam, the oxygen index is larger than 30%. The composition and the phosphorus-containing copolyester foam can be used for sandwich foam core materials with a high fire-proof requirement in the fields such as rail traffic, vehicles, aviation, ships, industry, furniture and the like as well as structural and thermal-insulation double-function materials for buildings.

Description

A kind of method that compositions preparing phosphorous copolyester foam and use said composition prepare phosphorous copolyester foam

Technical field

The invention belongs to new material technology field, be specifically related to a kind of compositions preparing phosphorous copolyester foam and the method using said composition to prepare phosphorous copolyester foam。

Background technology

Polyester belongs to combustible material, and it is when burning, the phenomenon such as HRR is big, calorific value is high, flame propagation speed, melted drippage。This characteristic makes it nevertheless suffer from certain restriction in the application of some key areas (such as track traffic, transport, building, electronic device, the vehicles, health care etc.)。

Since nineteen seventies, fire-retardant research and the application and development of polyester are become increasingly active by countries in the world, and modified mainly the taking of flame retardant type polyester is added wherein such as the fire retardant such as halogen and phosphorus compound。Existing research shows, containing halogen element, although particularly fire retardant chloride, bromine comparatively effectively and is widely used, but time easily discharge zest and corrosive gas, such as hydrogen halides, two English etc., make people suck and suffocate, thus being also that the application of halogen containing flame-retardant is restricted；Existing research shows, phosphorus is one of maximally effective polyester flame-retardant element (Wang Yuzhong is outstanding, the flame-retarded design of polyester fiber, Sichuan Science Press, 1994)。Phosphorus flame retardant pyrolysis when being heated is phosphoric acid, is finally translated into poly-Metaphosphoric acid or the pyrophosphoric acid class product of glassy state, forms sealing coat at material surface, stops heat transmission, reduces imflammable gas burst size and isolation air, reaches fire-retardant purpose。Certainly, fire retardation is difficult to be realized by certain single fire retardant mechanism, often appears as the comprehensive coordination effect of number of ways。

For the flame resistant method of polyester and polyester fiber, by the feed postition of production process and fire retardant, following several ways can be divided into:

Blending fire retardant modifiies: adds fire retardant to polyester system, does not change polyester production process；

Fire retardant is grafted polyester modified: make itself and reactive flame retardant generation Surface grafting reaction reach fire-retardant purpose on polyester fiber or fabric；

Flame-retardant after-finishing: fabric is placed in fire resistant fluid the dipping regular hour, takes out and dries。

Composite spinning is flame-retardant modified: carry out composite spinning with conventional polyester with the polyester containing flame-retardant composition。

Copolymerization is flame-retardant modified: adds reactive flame retardant in esterification or polycondensation phase and carries out copolycondensation。

Blending fire retardant modifiies, and can affect the persistency of fire resistance, it addition, fire retardant easily oozes out, human body and environment can be produced adverse effect。Fire retardant is grafted polyester modified and composite spinning is flame-retardant modified, and technical conditions 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 the feel of fabric, intensity, breathability and color and luster etc. are produced large effect, copolymerization is flame-retardant modified, owing to copolyreaction type phosphorus fire retardant has hydroxyl, carboxyl Liang Ge functional group, can join with alcohol, acid reaction in the strand of polyester, from molecular chain structure, give the fire resistance that polyester is good, and durability of fire-retardant is desirable。To sum up, phosphorous copolyester is the flame retardant polyester technology inherently giving polyester good flame-retardance energy of current scientific circles and industrial quarters 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 the structure of flame-retardant monomer and 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 constitutional repeating 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, it is preferable that 1.4-2.2dL/g, the content of the constitutional repeating unit of phosphor-containing flame-proof monomer is the 1-30% of this copolyesters constitutional repeating unit gross mass。

In this atactic polyester, the constitutional repeating unit A of phosphor-containing flame-proof monomer is at least one in following structure:

In formula, R₁For containing C₁-C₈Alkyl or phenyl or benzyl, R₂And R₃For C₁-C₈Alkylidene or aryl, the two can identical also can differ；X, Y and Z are O atom。The limited oxygen index of this phosphorous atactic polyester can reach 33%, has on the basis of excellent flame retardant performance, also improves its corresponding mechanical property, can be widely used for manufacturing thin film, bottle class, fire protecting clothing, tent, even fire-retardant high-strength industrial yarn。

US Patent No. 5602212 and US4981945 also disclose that a kind of phosphorous linear copolyester, and the constitutional repeating unit of its phosphor-containing flame-proof monomer is also the one in said structure。

Chinese patent CN201010602958.X discloses a kind of novel fire-retardant Thermotropic Liquid of 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, structural formula is as follows:

Chinese patent CN201010567685.X discloses a kind of fire-retardant blocked copolyester of phosphorous PTT, and what it was contained is at least one in following phosphorous glycol containing phosphorus component:

Or at least one of the phosphorous diacid diol ester that to be following phosphorous diacid prepare through esterification with ethylene glycol or 1,3-propylene glycol or 1,4-butanediol:

Or be in above-mentioned phosphorous glycol any one with phosphorous diacid diol ester in the mixture of any one。The oxygen index (OI) of the fire-retardant blocked copolyester prepared by method may be up to 33%。

Chinese patent CN200810045357.6 discloses a kind of phosphor-containing flame-retardant copolyester oligomer and preparation method thereof, and its flame-retardant monomer used is the compound being structured with formula:

In formula, R₁For C₁-C₁₂Alkyl, aryl or benzyl；R₂For C₁-C₈Alkylidene or aryl；X is O atom,

Or the assorted luxuriant and rich with fragrance compounds of 9,10-dihydro-9-oxy assorted-10-phosphinylidyne for being structured with formula:

In formula, R₃For propane-1，2，3-triyl, Y is O atom, Z₁、Z₂For hydroxy-acid group or ester group, Z₁、Z₂Can be identical, it is also possible to differ。

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:

The preparation method that Chinese patent CN200910058655.3 discloses a kind of phosphorus series non-halogen flame-proof copolyester, mating the requirement up to high fire-retardances such as 94ULV-0 level or VTM-0 level films of the phosphorus series non-halogen fire-retardant rank of flame retardant polyester polymer product for preparing by raw material and technique, limited oxygen index (LOI) is up to more than 45%。94ULV-0 level or the raw material of VTM-0 (being referred to as V0 level) thin film, fire-retardant I level and above fire resistance fibre and V0 level flame retardant plastics goods can be reached as producing fire resistance。Its described halogen-free phosphorus-containing copoly type fire retardant is the compound with below formula structure:

In formula, R is C₁-C₁₅Fisher's formula or cyclic alkyl, R ' is alkyl (C₁-C₅) or C₆-C₉Aryl or benzyl。

Chinese patent CN00135411.6 discloses a kind of phosphorus content in phosphorous copolyester that improves taked to facilitate blended processing phosphor-containing flame-proof polyester and goods thereof and 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, R₁: C₁-C₆Alkyl or C₆-C₉Aryl；R₂: C₁-C₆Alkylidene；R₃: H, C₁-C₆Alkyl or the hydroxyalkyl of correspondence；R₄: H, C₁-C₆Alkyl or the hydroxyalkyl of correspondence。US Patent No. 5602212 also discloses that 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, R₁、R₂For H atom or C₁-C₁₈Fisher's formula or cyclic alkyl, R₁、R₂Can be identical, it is also possible to differ；R₃Functional group's group for forming ester group (is structured with formula: COOR₅Or OR₅, wherein R₅For H atom or the C at least containing a hydroxyl₁-C₁₂Alkyl)；A₁For C₁-C₁₂Alkylidene。

US Patent No. 04737567 discloses a kind of phosphorous atactic polyester, and its phosphorous repeat unit structure is as follows:

In formula, Ar₁Represent 3 valency aromatic groups, for the alkyl group of H atom or 1-20 carbon atom or the aromatic alkyl group of alkoxy grp or 6-20 carbon atom or aralkyloxy groups, for instance can be following phosphor-containing flame-proof monomer:

US Patent No. 5650531 discloses a kind of high content of phosphorus halogen-free flameproof oligomer and preparation method thereof。Described phosphorus-containing compound has below 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 formula₁The alkyl group with hydroxyl for H atom or 1-10 carbon atom；R₂And R₃Alkyl group for halogen atom or 1-10 carbon atom；M and n represents the integer of 0-4。Concrete molecular formula can be following:

Also have on phosphorus flame retardant, introduce nitrogen element or phenyl raising flame retardant effect。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 the PET hue of a kind of production is good, the preparation method with the flame-retarding phosphorus copolymerized polyester of good form and aspect of excellent fireproof performance。The phosphorus flame retardant of its use is the one or more than one with following 3 kinds of general structures:

Wherein R₁For alkyl group or the alkoxy grp of nitrogen-containing group or 1-15 carbon atom, R₂For the alkyl group of 1-9 carbon atom, R₃And R₄Representing alkyl group or the alkoxy grp of 1-15 carbon atom, m and n represents the integer of 0-4, when the integer that m is 2-4, there is multiple R₃Can be same to each other or different to each other；When the integer that n is 2-4, there is multiple R₄Can be same to each other or different to each other；A represents the alkyl group containing 3-6 carbon atom containing ester linkage or alkoxy grp。

Additionally, the class phosphonium flame retardant that US Patent No. 4587362, US4358045 and US4088205 also use Spirocyclic prepares phosphorous copolyester, being 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 have phosphorus at main chain and phosphorus two kinds of forms on side chain, currently used more be backbone chain type phosphorus fire retardant。Flame-proof copolyester can be random, block, grafting or replace flame-proof copolyester。

The oxygen index (OI) of the phosphorous copolyester resin that above-mentioned patent system is standby is at least 25%, what have can up to 45%, oxygen index (OI) about 21% much larger than conventional polyester, but, above patent achieves the polyester resin of effective flameproof effect and limited range of application, the application of the aspect such as such as fiber, thin film, bottle class and Fire Retardant Industry silk。But these have the polyester resin melt viscosity of flameproof effect low can not directly should for extrusion foaming, thus these patents cover foamed materials range of application also without any requirement。

Due to general purpose grade polyester, the melt viscosity such as p-phthalic acid hexylene glycol ester (PET) and phosphorous copolyester is low, and during for extrusion foaming, abscess is easily rupturable and can not become desirable foamed materials。Research later finds by using suitable coupling agent can connect side chain on linear strand and then improve molecular weight and melt viscosity thereof。This development makes to produce thermoplastic polyester foam by extrusion and foaming process and is possibly realized。Branching coupling agent is the chemical substance containing multiple reactive functionality, it is possible to carries out condensation reaction with plural strand and produces branch polymer。Melt extrude branched chain polyester and suitable chemistry, physics or inert gas blown agent can make hole-closing structure foam。

US Patent No. 522932 discloses a kind of method of polyester extrusion foaming, in polycondensation process, adds the reactive functionality branching agent more than 2。Branching agent make consumption in 1.5-6 equivalent concentration of every 100 mole of diacid。By polycondensation reaction, the PET resin of branching is formed。Then this branched resin is used to carry out extrusion foaming。

A kind of method that US Patent No. 4132707 and US5422381 etc. disclose polyester extrusion foaming, adopts for general purpose grade and the PET resin reclaiming level, melt extrudes and give blended method first by resin and branching agent Homogeneous phase mixing pelletize。Then solid particle be heated under vacuum or nitrogen protection 170-220 DEG C then maintain temperature complete solid-state branching reaction to certain time。The PET resin prepared through solid-state upgrading reaction can be used to carry out extrusion foaming。

US Patent No. 5000991 discloses a kind of use branching agent and general purpose grade or recovery level PET resin melt blending in an extruder, the method being then directly added into foaming agent extrusion foaming at same machine back segment。The course of processing, equipment investment and production time can be reduced in this way。But the reaction efficiency of branching agent does not have first two method high, and the content remaining branching agent in froth pulp is also higher, and these residues seriously reduce the fire protecting performance of foam。In order to improve this technical process, US Patent No. 5696176 branching agent mother material is developed。Mother material is to use polyethylene or polypropylene to make masterbatch as the branching agent of carrier Yu high concentration is blended, then uses this masterbatch and general purpose grade or the recovery common extrusion foaming of level PET resin。

Chinese patent CN200910302063.1 discloses a kind of method utilizing bottle level PET foaming preparation PET sheet, it improves PET melt viscosity and intensity by adding the means of the acrylate multipolymer of polyfunctional group high active substance and nucleocapsid structure, add CBA, preparing 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 foamed product, and the molecular weight of the polyester adopt epoxy radicals coupling agent to improve the PET type resin with lower molecular weight and fragility, particularly reclaiming also improves its melt strength and swelling prepares。This foamed product can be used as padded coaming, insulant, packaging material, food containers and distribution material etc.。

Chinese patent CN98804872.8 also discloses that the foam of polyester foamed method and preparation。The polyester raw material realization of 0.8dl/g and interpolation foaming agent it is at least by extrusion molding intrinsic viscosity。This expanded polyester is such as manufacturing plate, thin plate and the pipe particularly used in building and encapsulation field。

Chinese patent CN200980121758.8, disclose a kind of pre-composition adding thermoplastic elastomer (TPE) and tetracarboxylic dianhydride in polyester resin, and it being foamed into foams, this foam contains the thermoplastic polyester elastomer that 0.5-15 weight is made a gesture of measuring, and makes the tear type variable of polyester form increase。

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, such 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 significantly improving after low-density core combines the relative rigidity of skin material with skin material, and the weight increase of unit are is only small。By selecting the combination of suitable skin material and core, 3% core that weight is skin material weight can be respectively increased bending strength 3.5 times and bending stiffness 7 times。

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 composite core thickness doubles, its bending strength increases by six times, and bending stiffness increases twelvefold。

In core filled composite material, the combination property of core is extremely important。The ideal performance of core includes high strength and stiffness, low-density, good chemically-resistant solvent and thermostability and low price etc.。The performance in actual applications of one core can be predicted by it is carried out laboratory test。These tests include compression, stretch and shearing test, and its performance indications include intensity, modulus and anamorphic stretching rate etc.。In structure sandwich material industry, the most frequently used core has cork wood, honeycomb texture core, thermoplasticity and thermosetting foams core etc.。

But the polyester form made by above-mentioned patent process is frequently not suitable for doing sandwich material, because its foam aperture is too big, and pore-size distribution is too wide, which results in poor mechanical performance。In the foaming process that above-mentioned patent provides, the polyester fondant being mixed with the collateralization of volatile organic foaming agent or noble gas is extruded through in the extrusion die entrance atmospheric environment of an annular or slit opening。In atmospheric pressure state, foaming agent expanding polyurethane melt and become foaming structure。As produced the thickness reaching conventional sandwich material requirement, then the problems such as excessive expansion is made the abscess-size of foamed products excessive by foaming agent, the even irregular surface of skewness。

US Patent No. 7951449 discloses a kind of method that extrusion prepares 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 arrange consistent those by bubble bars of they extrusions, merge mouth die boundling technology by bar bubble, it is possible to combination closely is then melted as the cystosepiment without any space。This section of patent makes PET be possibly realized as sandwich structure material, and first pushed market by 3A company of Switzerland in 2005, Sweden DIAB, BASF, the Britain GURIT of Germany and the foam core material manufacturer that several families are important in the world such as Armacell of Belgium have also released one after another respective PET foam core material obtain corresponding market, such as the field such as wind electricity blade and track traffic。

Polyester construction foam has a microcellular structure of trickle abscess, desirable dimensional stability, heat stability, chemical stability, excellent mechanical mechanics property, barrier property (heat-insulation and heat-preservation), anti-ultraviolet, water absorption is low, and its environmental friendliness, it is easy to recycling。Just because of above-mentioned good characteristic, conventional polyester foam is widely used in packaging field (food, medicine, electronics etc.)。PET construction sandwich foamed materials is at industrial circle (sports equipment, container etc.), field of track traffic (floor, hood etc.), boats and ships (deck, internal structure etc.), the field such as wind energy (blade, engine room cover etc.) and building obtains good application。But above-mentioned foam does not have, or only there is relatively low fire protecting performance, substantially do not reach the fire protection requirement of China's building industry。

Current China is newly-increased construction area about 2,000,000,000 square metres every year, and wherein the completed floor space of building curtain wall is 75,000,000 square metres。Building curtain wall is substantially sandwich structure composite board, and using sandwich material area is 22,500,000 square metres, and 2012 annual requirements are up to 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 specifically includes that EPS, XPS, polyurethane, rock wool, glass cotton, plank, foam concrete etc.。Can not reasonably unifying in environmental-protecting performance, mechanical property, processing characteristics, heat-insulating property, fire protecting performance, weather resistance and application property etc., respective pluses and minuses are obvious。Light foam heat-barrier material therein does not all reach desirable fire protection requirement。

Day by day improve along with people's level of consumption, building industrialization level and building energy conservation requirement etc., the enhancing day by day of environmental consciousness, the concept day of low-carbon emission reduction enters the popular feeling, it is desirable to New Building Materials develop to safe and environment-friendly, energy-conservation, waterproof, high-quality, the complex function direction such as attractive in appearance。Make the structural type construction wall of 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 and parts have become a kind of development trend。The energy saving building curtain wall such as made with sandwich material, it is possible to alleviate wall weight, improves the effect that wall thermal insulating is heat insulation, and has good sound insulation, fire-retardant and corrosion resistance。Additionally by adjusting structure, it is also used as materials for wall, such as house inner wall and the quick body of wall assembling room, these quickly assemble room and may be used for disaster relief and rescue, building site barracks, are also beneficial to builder and build general house faster, and this has subversive meaning at building materials field。

Market generally believes that polyester construction foam core material can be used as, at building field, the new material that insulation is combined with mechanical property, it is possible to substitute above-mentioned existing high-strength, lightweight, heat insulation, fire proofing material for building。Polyester construction foam core material uses as building, and precondition must is fulfilled for Building Fire Protection requirement。Commercially available stagnant combustion, the polyester construction foam core material of low cigarette, simply meet the requirement about fire protecting performance of the DIN5510 of field of track traffic, but its oxygen index (OI) only has about 26%, do not reach fire-retardant rank, i.e. oxygen index (OI) and be not less than the requirement of 28%, just substantially limit its application having high fire protection requirement field in building etc.。

To sum up, (1) has that the phosphorous copolyester resin melt viscosity of flameproof effect is low can not be used directly to extrusion foaming so that it can only apply in such as fiber, thin 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 oxygen index (OI) and be not less than the application requirement of 28%。

In the past few decades, utilize single double screw extruder to react extrusion modification by copolymerization and be widely used in the processed and applied of thermoplastic polymer。It is one of successful case by reactive extrursion branching stated polyesters resin。U.S. Patent application 20100201015 discloses a kind of application response extrusion molding and prepares PET graft copolymerization ester and the method for molding product。Preparing phosphorous copolyester thereby through reactive extrursion method, then to carry out foaming will be more preferably method。

Summary of the invention

Invention broadly provides a kind of grade phosphorous copolyester compositions and method of preparing phosphorous copolyester foam thereof of foaming, oxygen index (OI), more than 30%, can be used as the sandwich foam core material of high fire protection requirement (such as track traffic, vehicle, aviation, boats and ships, industry and furniture etc.) and building structure and heat-insulation and heat-preservation bifunctional material。Its technical scheme is as follows:

A kind of foaming level phosphorous copolyester compositions, it includes the component of following weight portion: 100 parts of general purpose polyesters, 0.1-30 part reactivity phosphonium flame retardants, 0.1-15 part viscosifier, 0.1-15 part foaming agent and 0-8 part nucleator；In above-mentioned foaming level phosphorous copolyester compositions, phosphorus content is 5000-20000ppm, IV value is 1.10-1.40dL/g。When IV value is lower than 1.10dL/g, foaming effect is bad, too high higher than 1.40dL/g then cost。

Preferably, described foaming level phosphorous copolyester compositions, it includes the component of following weight portion: 100 parts of general purpose polyesters, 5-20 part reactivity phosphonium flame retardants, 5-10 part viscosifier, 5-10 part foaming agent and 2-5 part nucleator；In above-mentioned foaming level phosphorous copolyester compositions, phosphorus content is 8000-15000ppm, IV value is 1.20-1.40dL/g。

Preferably, the mixture of described general purpose polyester a kind of or they arbitrary proportions in PET polyester (polyethylene terephthalate), PBT polyester (polybutylene terephthalate (PBT)), PTT polyester (PTT), PEN polyester (PEN) and PCT polyester (poly terephthalic acid Isosorbide-5-Nitrae-cyclohexane dicarboxylates)。Prioritizing selection uses PET polyester。

Preferably, the mixture of described phosphonium flame retardant a kind of or they arbitrary proportions in the acid of hydroxy phenyl phosphinylidyne, carboxyalkyl phenyl hypophosphorous acid, 2-hydroxymethyl phosphoric acid and its carboxylate, triphenyl phosphate, poly phosphate, high content of phosphorus halogen-free flameproof oligomer, fragrance poly phosphate, response type phosphorus silicon fire retardant, phenyl hypophosphorous acid metal salt and polyphenylene phosphoric acid diphenyl sulphone (DPS) ester。

Hydroxy phenyl phosphinylidyne acid can be hydroxy phenyl phosphonoacetic acid, hydroxy phenyl phosphinylidyne propanoic acid and hydroxy phenyl phosphinylidyne butanoic acid。The hydroxy phenyl phosphinylidyne propanoic acid of preferred solid forms and butanoic acid。

Shown in the following formula I of structural formula of hydroxy phenyl phosphinylidyne propanoic acid:

2-hydroxymethyl phosphoric acid and its carboxylate can be shown in following formula II and (III):

Shown in the following formula IV of poly phosphate, shown in fragrance poly phosphate such as following formula (V):

High content of phosphorus halogen-free flameproof oligomer repetitive containing

With:

Can also be:

Wherein, R isN is the integer of 0-10。

Response type phosphorus silicon fire retardant as:

Phenyl hypophosphorous acid metal salt as:

The polyphenylene phosphoric acid diphenyl sulphone (DPS) ester of solid crystal as:

Preferably, the density of described phosphorous copolyester foam is 30-950kg/m³, it is preferred that for 30-650kg/m³；

The mixture of described foaming agent a kind of or they arbitrary proportions in noble gas, aliphatic hydrocarbon, saturated alicyclic hydrocarbon, halothane hydrocarbon, ether and ketone。Described foaming agent, it is possible to use known various foaming agent, for instance CBA and physical blowing agent。CBA is mainly can the foaming agent of high temperature thermal decomposition, for instance the thermal decomposition of blowing agent of various organic or inorganics。Organic foaming agent, for instance nitroguanidine, oxalyl hydrazine, toluene yellow line semicarbazides, 5-phenyltetrazole, carbonyl amide and diisopropyl azodicarboxylate etc.；Inorganic foaming agent, for instance barium azodicarboxylate, azo-2-carboxylic acid's strontium, aluminium hydroxide, magnesium hydroxide, bicarbonate and citric acid systems etc.。CBA likely produces to promote the small molecule by-product of flame-proof copolyester degraded in catabolic process, and the decomposition temperature of CBA mates requirement height with the processing temperature of phosphorous copolyester, it is advantageous to physical blowing agent。Physical blowing agent, including noble gas, for instance carbon dioxide, nitrogen, argon and compression air etc.；Aliphatic hydrocarbon, for instance propane, butane, pentane, iso-butane, neopentane, isopentane, hexane and butadiene；Saturated alicyclic hydrocarbon, for instance hexamethylene；Tetrafluoroethane, hydrogenation fluorochlorohydrocarbon and (hydrogenation) halothane hydrocarbon；Ether, for instance methyl sec-butyl ether；Ketone, for instance acetone。These can be used alone, it is also possible to arbitrary proportion mixing uses。From the viewpoint of environmental protection, it is preferred to use noble gas, the solubility factor for resin, more preferably carbon dioxide and nitrogen。

The mixture of described nucleator a kind of or they arbitrary proportions in Pulvis Talci, calcium carbonate, calcium oxide, Kaolin, barium sulfate, silicon dioxide and aluminium oxide。

Preferably, described viscosifier are chain extender or tackifier masterbatch 0.1-30wt% chain extender and 70-99.9wt% vector resin melting mixing obtained；

Preferably, the mixture of described chain extender a kind of or they arbitrary proportions in polyfunctional group isoxazoline compound, polyfunctional isocyanate, multi-functional epoxy compound, multifunctional anhydride and polyphosphate compound。Chain extender is mainly for improving the melt strength of polyester so that it is suitable foaming。Utilize the reactive group in chain extender to carry out grafting, coupling or cross-linking reaction with the reactive group in polyester chain, improve melt strength, to meet cell stabilization。

Wherein, polyfunctional group isoxazoline compound can be aromatic compounds can also be aliphatic compound。It it is such as ortho position, between position, or the phenylene bis-oxazoline of para-orientation, 2, double, two (the 2-azoles quinoline-2-base) pyridine (and there is the derivant of alkyl or aryl substituent group on oxazoline ring) of 6-, 2, double, two (the 8H-indeno [1 of 6-, 2-d] azoles quinoline-2-base) pyridine, 1, 2-double, two (4, 4-dimethyl-2-azoles quinoline-2-base) ethane (and there is the derivant of alkyl or aryl substituent group on oxazoline ring), 2, the block copolymer of the double, two-2-azoles quinoline (and there is the derivant of alkyl or aryl substituent group on oxazoline ring) of 2-isopropyl and at least two Alpha-Methyl vinyl-2-azoles quinoline unit composition, such as 1, 3-penylene-bis-(2-azoles quinoline), double, two (2-azoles quinolines), 1, 4-penylene-bis-oxazoline, 2, 2-double, two (2-azoles quinoline) etc.。

Polyfunctional isocyanate is diisocyanate aliphatic, alicyclic, aromatic or polyisocyanate such as。The available polyisocyanate containing the sub-amide groups of carbonization two, carbamic acid base, allophanic acid base, cyamelide base, urea element base or biuret groups, these can be described as " modified polyisocyanate " or " isocyanate prepolymer "。Such as 1,8-diisocyanato-p-methane, methyl diphenylene diisocyanate, cyclohexyl diisocyanate, phenylene diisocyanate, toluene di-isocyanate(TDI) (include 2,4-toluene di-isocyanate(TDI), 2,6-toluene di-isocyanate(TDI) and crude tolylene diisocyanate), methyl diphenylene diisocyanate, chlorophenylene diisocyanates, diphenyl methane-4,4 '-diisocyanate is (also referred to as 4,4 '-methyl diphenylene diisocyanate), naphthalene-1,5-diisocyanate；Polymethylene multi-phenenyl isocyanate；Hexamethylene diisocyanate homopolymerization trimer, toluene di-isocyanate(TDI) homopolymerization trimer, different Buddhist diisocyanates homopolymerization trimer, 4,4 '-diphenyl methane-diisocyanate homopolymerization trimer, methyl diphenylene diisocyanate homopolymerization trimer, 4,4-dicyclohexyl methyl hydride diisocyanate homopolymerization trimer, fourth diisocyanate homopolymerization trimer, pungent diisocyanate homopolymerization trimer, the last of the ten Heavenly stems diisocyanate homopolymerization trimer and the homopolymerization trimer such as naphthalene diisocyanate homopolymerization trimer；Oneself two Carbimide .s, toluene di-isocyanate(TDI), different Buddhist diisocyanates, 4,4 '-diphenyl methane-diisocyanate, tercopolyureas aggressiveness between methyl diphenylene diisocyanate and 4,4-dicyclohexyl methyl hydride diisocyanate；Ethyl phosphonic acid diisocyanate, C₂H₅P(O)(NCO)₂, phosphenylic acid diisocyanate, C₆H₅P(O)(NCO)₂, compound containing trivalent silicon cyanate group, the compound such as the isocyanates that formed by sulfonamide, cyanic acid and Hydrogen thiocyanate the mixture of one or more arbitrary proportions。

Multi-functional epoxy compound refers to contain in the molecule the compound of two or more epoxide groups。Including aliphatic compound, such as Polyethylene Glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol 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) adipate ester, four epoxy glycerite bis aminomethyl hexamethylene etc.；Heterocyclic compound, for instance diglycidyl hydantoin, diglycidyl base oxyalkyl hydantoin, three epoxy glycerite Carbimide. urea acid esters, three epoxy glycerite cyanates, three epoxy glycerite hydantoin etc.；Aromatic compounds, for instance diglycidyl ethers of bisphenol-A, p-phthalic acid diglycidyl ether initial condensates, diphenyl methane diglycidyl ether, p-phthalic acid diepoxy glyceride, M-phthalic acid, the p-or m-amino-phenol of three Synthesis of Oligo Ethylene Glycol, four epoxy glycerite benzyl ethane, sorbitol four Synthesis of Oligo Ethylene Glycol, four epoxy glycerite tetramethyl triaminotriphenyl methane NH2s, cresol novolak epoxy resin etc.。

In above-mentioned chain extender, from aspects such as the convenience to the hazardness of human body and use, it is preferred that polyfunctional epoxy compound and polyfunctional group anhydride, it is especially preferred that dicarboxylic anhydride。Preferred dicarboxylic anhydride is the dicarboxylic anhydride of following tetrabasic carboxylic acid: 1,2,4,5-benzenetetracarboxylic acid, Pyromellitic Acid, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid, 2,2-pairs-(3,4-dicarboxyphenyi)-propane, double; two-(3,4-dicarboxyphenyi)-ether, double; two-(3,4-dicarboxyphenyi)-thioether, double; two-(3,4-dicarboxyphenyi)-sulfone, double; two-(3,4-dicarboxyphenyi)-sulfoxide, naphthalene-2,3,6,7-tetrabasic carboxylic acid, oxolane-2,3,4,5-tetrabasic carboxylic acids, 2,2-pair-(3,4-dicarboxyphenyi) HFC-236fa, 1,2,5,6-naphthalene tetracarboxylic acids and mixture thereof。Particularly preferred dicarboxylic anhydride is pyromellitic acid anhydride。

The mixture of described vector resin a kind of or they arbitrary proportions in vistanex, conjugated polyester resin, nylon resin and polycarbonate resin。Described vector resin is close with the processing temperature of general purpose polyester, and thermostability is high, keeps more than 10min not decompose, have a resinoid of mobility at 300 DEG C。

Preferably, the mixture of described vector resin a kind of or they arbitrary proportions in acrylic resin, maleic acid graft polypropylene, Merlon and PETG resin。

The reaction that in the present invention, polyester resin, the phosphorous combustion agent of response type and chain extender occur in reactive extrursion process can be that the combination of ester exchange, grafting, chain extension and cross-linking reaction is to prepare phosphorous copolyester。Its P elements can on main chain, it is also possible to be on side chain。Course of reaction improves polyester fondant intensity and melt viscosity simultaneously。Thus forming stable foam structure after introducing foaming agent。

A kind of grade method that phosphorous copolyester compositions prepares phosphorous copolyester foam that foams, comprise the following steps: by the general purpose polyester of formula ratio, reactive phosphonium flame retardant, viscosifier, foaming agent and nucleator are under the melt temperature of general purpose polyester, modifiied by extruder reactive blending, by die extrusion foaming, obtain phosphorous copolyester foam, more this foam is drawn, cuts, namely prepare finished product。

The feature of above-mentioned one-step method is that reaction, thickening and foaming one step complete, and reduces equipment investment, and production efficiency is high。

The method that another kind of foaming level phosphorous copolyester compositions prepares phosphorous copolyester foam, comprises the following steps:

(1) by the general purpose polyester of formula ratio, reactive phosphonium flame retardant, viscosifier mixing, reactive extrursion pelletize under the melt temperature of polyester；

(2) particle made in step (1) being carried out high temperature solid-state reactions, this process completes the phosphorous copolyester of branching reaction preparation foaming level；

(3) phosphorous copolyester of foaming level, the foaming agent of formula ratio and nucleator step (2) obtained passes through extruder melting mixing, by die extrusion foaming, obtain phosphorous copolyester foam, more this foam is drawn, cuts, namely prepare finished product。

The feature of above-mentioned two-step method is that technique is long, and phosphonium flame retardant and chain extender consumption are few, react completely, foamed product good flame retardation effect。

Phosphorous copolyester of the present invention, before mixing with viscosifier, it is desirable to moisture, at below 30ppm, at least need to dry four hours at 160 DEG C。

The high temperature solid-state reactions described in step (2) in present invention, in two-step method, it is possible to vacuum or noble gas (such as nitrogen, argon etc.) are heated to 120-230 DEG C under protecting, and maintain temperature 1-30 hour。

In present disclosure, one-step method and the mouth die described in two-step method include rectangle die lip, ring-type mouth die, T-shaped mouth die, circular mouth die, foraminous die plate (bar bubble boundling mouth die) and other abnormity mouth die etc.。

In present disclosure, extrusion equipment described in one-step method and two-step method, including single screw extrusion machine and tandem, double screw extruder and tandem, single double screw extruder mixing tandem, it may be necessary to add smelt gear pump between two extruders。

As required, present disclosure also can add nucleator commonly used in the art, in two-step method, nucleator is added in step (1), can also add in step (3), addition form can be directly added into, it is also possible to adds with masterbatch (nucleator masterbatch that namely 0.1-30 part nucleator and the 70-99.9 part vector resin melting mixing obtain) form known to art technology。Nucleator can be used to promote the heterogeneous nucleation of polyester of the present invention, adjusts cell density and abscess-size。

Additionally, other additives can also be used for this invention, these additives include: impact modifying agent, filler, stabilizer, antioxidant, antistatic additive, coloring agent, fuel and pigment。These additives, their consumption and their purposes are well known in the art。

Adopting phosphorous copolyester foam prepared by reactive extrursion flame retardant polyester foam composition material producing, molding, after sawing, trimming etc. are processed further, a number of leftover pieces can be produced, do not recycle and can cause the wasting of resources, so environmental pollution, it is necessary to it is melted and is recycled。But, phosphorous copolyester is after extrusion foaming, and its IV value can decline, it is possible to can not be used directly to extrusion foaming because melt strength is low, and the mode adding chain extender can be adopted to improve its melt strength and melt viscosity。In active reaction group in chain extender and leftover pieces reactive group (such as hydroxyl, carboxyl etc.) carry out grafting, coupling or cross-linking reaction, make strand lengthen or produce side chain, improve molecular weight, thus improving melt strength and melt viscosity, to meet cell stabilization。So both can ensure that the smooth of the phosphorous copolyester extrusion and foaming process that with the addition of leftover pieces, it is also ensured that the phosphorous copolyester foaming properties of preparation meets instructions for use。These leftover pieces add with the consumption of the 0.1%-50% relative to phosphorous copolyester weight。

The present invention adopts phosphorous copolyester foam prepared by reactive extrursion flame retardant polyester foam composition material to have excellent fire protecting performance, and the B level burning behavior class requirement of " construction material and product burns grading performance " standard can be met, oxygen index (OI) is more than 30%, can be used as the sandwich foam core material of high fire protection requirement (such as track traffic, vehicle, aviation, boats and ships, industry and furniture etc.) and building structure and heat-insulation and heat-preservation bifunctional material, be with a wide range of applications。

Adopt above-mentioned foaming level phosphorous copolyester compositions and the method preparing phosphorous copolyester foam thereof, the invention have the advantages that

(1) present invention adopts conventional polyester and the reacted extrusion of response type phosphonium flame retardant prepare flame retardant polyester and foam, and technological process is short, and cost is low；

(2) the phosphorous copolyester foam that the present invention prepares has an excellent fire protecting performance, and can meet the B level burning behavior class requirement of " construction material and product burns grading performance " standard, and oxygen index (OI) is more than 30%；

(3) the phosphorous copolyester foam that the present invention prepares can be used as the sandwich foam core material (such 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。

Detailed description of the invention

Embodiment 1

One-step method prepares phosphorous copolyester foam

1. material selects: general common grade polyester chip is selected from PET polyester, that concrete is the WB-8816 of China Resources polyester (Changzhou) company limited, its IV value is 0.8dL/g, polyphenylene phosphoric acid bisphenol-A ester (Sichuan Union University experimental products), viscosifier are triphenyl phosphate, foaming agent is carbon dioxide, and nucleator is that Pulvis Talci, viscosifier and nucleator dry 6 hours at 160 DEG C respectively in dehumidifying heat pump。

2. preparation method: by 100 weight portion general common level polyester, 15 weight portion poly phosphates, 3 weight portion viscosifier and the 0.3 weight portion nucleator double screw extruder mix homogeneously adding gear pump, reaction modifying under the melt temperature of general purpose grade polyester, 2 parts of foaming agent portions in an extruder add。Containing foaming agent melt by foraminous die plate, through beaming device, the width obtaining merging is 10cm, thickness is 5cm, and density is 120kg/m³Polyester form sheet material。The rate of feeding of general purpose grade polyester is 20kg/h。Extruder technological parameter is in Table 1, and the performance parameter of gained polyester form is in Table 3。

Table 1 extruder technological parameter

Embodiment 2

Two-step method prepares phosphorous copolyester foam

1. material selects: general purpose polyester is PBT polyester, response type phosphorus level fire retardant is 2-carboxyethyl phenyl hypophosphorous acid (white solid, Qingdao Fu Silin Chemical Industry Science Co., Ltd product), viscosifier are acrylic resin and the mixture of maleic acid graft polypropylene, foaming agent is nitroguanidine and the mixture of 5-phenyltetrazole, nucleator is calcium carbonate, dries 6 hours respectively in dehumidifying heat pump at 160 DEG C。

2. preparation method: by 100 weight of polyester, 0.1 weight portion 2-carboxyethyl phenyl hypophosphorous acid, 2 parts by weight of polypropylene resins, the reactive extrursion pelletize at 265 DEG C of 3 parts by weight of maleic graft polypropylenes, pre-crystallized after drying, it is placed in rotary drum tackifying equipment, solid-state reaction 6h at 200 DEG C of temperature, preparation foaming level phosphorous copolyester。Dried foaming level phosphorous copolyester 100 weight portion, 0.8 weight parts of calcium carbonate nucleator and 1 weight portion nitroguanidine, 2 weight portion 5-phenyltetrazoles, by extruder mix homogeneously, 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 110kg/m³Phosphorous copolyester foam board。The rate of feeding of polyester is 20kg/h。Extruder technological parameter is in Table 1, and the performance parameter of gained polyester form is in Table 3。

Embodiment 3

One-step method prepares phosphorous copolyester foam

1. material selects: general purpose polyester is PTT polyester, reactive phosphonium flame retardant is the mixture of triphenyl phosphate, poly phosphate, polyphenylene phosphoric acid diphenyl sulphone (DPS) ester, viscosifier are 2, double; two (the 2-azoles quinoline-2-base) pyridine of 6-, 1,8-diisocyanato-p-methane, PETG resin mixture, nucleator is that the mixture of aluminium oxide and silicon dioxide, viscosifier and nucleator dry 5 hours at 145 DEG C respectively in dehumidifying heat pump。

By 100 weight portion PTT polyester, 7 parts by weight of phosphoric acid triphenylmethyl methacrylates, 6 weight portion poly phosphates, 9 weight portion polyphenylene phosphoric acid diphenyl sulphone (DPS) esters, 1.5 weight portions 2,6-double; two (2-azoles quinoline-2-base) pyridine, 1.5 weight portions 1,8-diisocyanato-p-methane, 7 weight portion PETG resins and 1 parts by weight of alumina and the 1 parts by weight of silica double screw extruder mix homogeneously adding gear pump, reaction modifying under the melt temperature of general purpose grade polyester, 5 weight portion propane, 5 weight portion methyl sec-butyl ether portions in an extruder add。Containing foaming agent melt by foraminous die plate, through beaming device, the width obtaining merging is 10cm, thickness is 5cm, and density is 30kg/m³Polyester form sheet material。The rate of feeding of general purpose grade polyester is 30kg/h。Extruder technological parameter is in Table 1, and the performance parameter of gained polyester form is in Table 3。

Embodiment 4

One-step method prepares phosphorous copolyester foam

1. material selects: general purpose polyester is PCT polyester, reactive phosphonium flame retardant is the mixture of polyphenylene phosphoric acid diphenyl sulphone (DPS) ester and hydroxy phenyl phosphonoacetic acid, viscosifier are the mixture of polypropylene glycol diglycidyl ether, pyromellitic acid anhydride and Merlon, foaming agent is the mixture of hexamethylene and aluminium hydroxide, nucleator is that the mixture of Kaolin and calcium oxide, viscosifier and nucleator dry 5 hours at 150 DEG C respectively in dehumidifying heat pump。

By 100 weight portion PCT polyester, 2 weight portion polyphenylene phosphoric acid diphenyl sulphone (DPS) esters, 3 weight portion hydroxy phenyl phosphonoacetic acids, 1.5 weight portion polypropylene glycol diglycidyl ethers, 1.5 weight portion pyromellitic acid anhydrides, 12 weight part polycarbonates, 2 parts by weight kaolin clay, the 3 weight portion calcium oxide double screw extruder mix homogeneously adding gear pump, reaction modifying under the melt temperature of general purpose grade polyester, 7 parts by weight of cyclohexane portion in an extruder adds。Containing foaming agent melt by foraminous die plate, through beaming device, the width obtaining merging is 10cm, thickness is 5cm, and density is 80kg/m³Polyester form sheet material。The rate of feeding of general purpose grade polyester is 25kg/h。Extruder technological parameter is in Table 1, and the performance parameter of gained polyester form is in Table 3。

Embodiment 5

Two-step method prepares phosphorous copolyester foam

1. material selects: general purpose polyester is PEN polyester and the mixture of PET polyester, reactive phosphonium flame retardant is the mixture of response type phosphorus silicon fire retardant and phenyl hypophosphorous acid metal salt, viscosifier are 1,2-double; two (4,4-dimethyl-2-azoles quinoline-2-base) mixture of ethane and diglycidyl ethers of bisphenol-A, nucleator is that calcium carbonate, viscosifier and nucleator dry 5 hours at 160 DEG C respectively in dehumidifying heat pump。

By 50 weight portion PEN polyester, 50 weight portion PET polyester, 15 weight portion response type phosphorus silicon fire retardants, 15 weight portion phenyl hypophosphorous acid metal salts, 4 weight portions 1,2-double; two (4,4-dimethyl-2-azoles quinoline-2-base) ethane, 4 parts by weight of bisphenol A diglycidyl ether reactive extrursion pelletizes at 270 DEG C, pre-crystallized after drying, it is 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 portion, 3 weight parts of calcium carbonate nucleators and 4 weight portion 5-phenyltetrazoles, 3 weight portion argon are by extruder mix homogeneously, 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/m³Phosphorous copolyester foam board。The rate of feeding of polyester is 25kg/h。Extruder technological parameter is in Table 1, and the performance parameter of gained polyester form is in Table 3。

Embodiment 6

One-step method prepares phosphorous copolyester foam

1. material selects: general common grade polyester chip is selected from PET polyester, that concrete is the WB-8816 of China Resources polyester (Changzhou) company limited, its IV value is 0.8dL/g, reactive phosphonium flame retardant is hydroxy phenyl phosphonoacetic acid and the mixture of polyphenylene phosphoric acid bisphenol-A ester, viscosifier are the mixture of pyromellitic acid anhydride and acrylic resin, foaming agent is the mixture of carbon dioxide and nitrogen, nucleator is that Pulvis Talci, viscosifier and nucleator dry 6 hours at 160 DEG C respectively in dehumidifying heat pump。

2. preparation method: by 100 weight portion PET polyester, 5 weight portion hydroxy phenyl phosphonoacetic acids, 5 weight portion polyphenylene phosphoric acid bisphenol-A esters, 0.02 weight portion pyromellitic acid anhydride, 11.98 parts by weight of polypropylene resins and the 1 weight portion Pulvis Talci double screw extruder mix homogeneously adding gear pump, reaction modifying under the melt temperature of general purpose grade polyester, 1 weight portion carbon dioxide and 1 weight portion nitrogen portion in an extruder add。Containing foaming agent melt by foraminous die plate, through beaming device, the width obtaining merging is 10cm, thickness is 5cm, and density is 650kg/m³Polyester form sheet material。The rate of feeding of general purpose grade polyester is 20kg/h。Extruder technological parameter is in Table 1, and the performance parameter of gained polyester form is in Table 3。

Embodiment 7

Two-step method prepares phosphorous copolyester foam

1. material selects: general purpose polyester is PBT polyester, response type phosphorus level fire retardant is 2-carboxyethyl phenyl hypophosphorous acid (white solid, Qingdao Fu Silin Chemical Industry Science Co., Ltd product), viscosifier are phosphonic acids triphenylmethyl methacrylate, foaming agent is carbon dioxide, and viscosifier dry 6 hours at 160 DEG C in dehumidifying heat pump。

2. preparation method: by 100 weight of polyester, 2 weight portion 2-carboxyethyl phenyl hypophosphorous acid, 0.1 weight portion phosphonic acids triphenylmethyl methacrylate reactive extrursion pelletize at 265 DEG C, pre-crystallized after drying, it is placed in rotary drum tackifying equipment, solid-state reaction 6h at 200 DEG C of temperature, prepares foaming agent phosphorous copolyester。Dried foaming agent phosphorous copolyester 100 weight portion and 0.1 weight portion carbon dioxide are by extruder mix homogeneously, 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 130kg/m³Phosphorous copolyester foam board。The rate of feeding of polyester is 20kg/h。Extruder technological parameter is in Table 1, and the performance parameter of gained polyester form is in Table 3。

Comparative example 1

1. material selects: general common grade polyester chip is selected from PET polyester, that concrete is the WB-8816 of China Resources polyester (Changzhou) company limited, its IV value is 0.8dL/g, viscosifier are triphenyl phosphate, foaming agent is carbon dioxide, nucleator is that Pulvis Talci, viscosifier and nucleator dry 6 hours at 160 DEG C respectively in dehumidifying heat pump。

By 100 weight portion general common level polyester, 3 weight portion viscosifier, 0.3 weight portion nucleator and 2 parts by weight of blowing agent carbon dioxide by double screw extruder mix homogeneously, modifiy 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/m³Polyester form sheet material。The rate of feeding of general purpose grade polyester is 30kg/h。Extruder technological parameter is in Table 1, and the performance parameter of gained polyester form is in Table 3。

Comparative example 2

Commercially available phosphorous copolyester (the fire-retardant slice (phosphorous in main chain) of such as Jinan Hao Ersen company, IV value is 0.67dl/g, phosphorus content is 5600ppm), viscosifier (without vector resin) and nucleator dry 4 hours at 160 DEG C respectively in removal moisture drying agent。

By 100 weight portion phosphorous copolyesters, 1.0 weight portion viscosifier (without vector resin), 2.0 parts by weight of blowing agent carbon dioxide and 0.3 weight portion Pulvis Talci by double screw extruder mix homogeneously, under the melt temperature of phosphorous copolyester, reactive extrursion modifiies, pass through foraminous die plate, through beaming device, the width obtaining merging is 10cm, thickness is 5cm, and density is 120kg/m³Phosphorous copolyester foam board。The rate of feeding of phosphorous copolyester is 20kg/h。Extruder technological parameter is in Table 2, and the performance parameter of gained polyester form is in Table 3。

Table 2 extruder technological parameter

Performance detection and result

The performance testing conditions used in above example and method are as follows:

Intrinsic viscosity (IV) Ubbelohde viscometer detects with the 6:4 mixed solvent of phenol Yu 1,1,2,2-sym-tetrachloroethane at 30 DEG C。

Phosphorus content method of testing: the phosphorous copolyester choosing more than 5 kinds different phosphate content is cut into slices as standard sample, it is measured with ICP (inductive high frequency plasma torch atomic emission spectrometry), the fluorescence intensity drawing standard curve according to phosphorus content and correspondence。When testing the phosphorus content of foaming level phosphorous copolyester, the fluorescence intensity according to the P elements of test, standard curve obtains the phosphorus content of correspondence。

Density detects according to ISO845。

Compression performance, according to ISO844-2007, detects on 100KN universal testing machine。

Cutting performance, according to ASTMC273, detects on 100KN universal testing machine。

Oxygen index (OI), according to GB/T2406.1-2008, detects on HC-2 type oxygen index measurer。

Embodiment and comparative example all prepare phosphorous copolyester foam on co-rotating twin screw extruder。This twin screw parameter is as follows: draw ratio is 40:1, and screw diameter is 49.2mm。This extruder is equipped with smelt gear pump, to improve flux foaming pressure。The mouth die of foam shaping by extrusion is foraminous die plate (bar bubble boundling mouth die)。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。

In embodiment 1-7 and comparative example 1-2, exruded foams performance measurement result is as shown in table 3:

Table 3 the performance test results

As shown in Table 3, the oxygen index (OI) of the phosphorous copolyester foam in embodiment 1-7 is all higher than 30%, it is better than in comparative example 1 and does not use the result using phosphorous copolyester to measure in phosphonium flame retardant and comparative example 2, in comparative example 2, phosphorous copolyester is commercially available, its IV value is generally relatively low, and the terminal functionality of polyester is occupied, when particularly phosphorus content is high (8000-15000ppm), viscosity is low especially, it is impossible to carry out one-step method or two-step method thickening smoothly。Thus illustrate that the foaming level phosphorous copolyester compositions of the present invention has excellent fire protecting performance, be suitable to extruder foaming。

It will be apparent to those skilled in the art that can technical scheme as described above and design, make other various corresponding changes and deformation, and all these change and deformation all should belong within the protection domain of the claims in the present invention。

Claims

1. preparing a compositions for phosphorous copolyester foam, it includes the component of following weight portion: 100 parts of general purpose polyesters, 0.1-30 part reactivity phosphonium flame retardants, 0.1-15 part viscosifier, 0.1-15 part foaming agent and 0-8 part nucleator；In above-mentioned foaming level phosphorous copolyester compositions, phosphorus content is 5000-20000ppm, IV value is 1.10-1.40dL/g。

2. the compositions preparing phosphorous copolyester foam according to claim 1, it includes the component of following weight portion: 100 parts of general purpose polyesters, 5-20 part reactivity phosphonium flame retardants, 5-10 part viscosifier, 5-10 part foaming agent and 2-5 part nucleator；In above-mentioned foaming level phosphorous copolyester compositions, phosphorus content is 8000-15000ppm, IV value is 1.20-1.40dL/g。

3. the compositions preparing phosphorous copolyester foam according to claim 1, it is characterised in that: the mixture of described general purpose polyester a kind of or they arbitrary proportions in PET polyester, PBT polyester, PTT polyester, PEN polyester and PCT polyester。

4. the compositions preparing phosphorous copolyester foam according to claim 1, it is characterised in that: the mixture of described phosphonium flame retardant a kind of or they arbitrary proportions in the acid of hydroxy phenyl phosphinylidyne, carboxyalkyl phenyl hypophosphorous acid, 2-hydroxymethyl phosphoric acid and its carboxylate, triphenyl phosphate, poly phosphate, high content of phosphorus halogen-free flameproof oligomer, fragrance poly phosphate, response type phosphorus silicon fire retardant, phenyl hypophosphorous acid metal salt and polyphenylene phosphoric acid diphenyl sulphone (DPS) ester。

5. the compositions preparing phosphorous copolyester foam according to claim 1, it is characterised in that: the density of described phosphorous copolyester foam is 30-950kg/m³；

The mixture of described foaming agent a kind of or they arbitrary proportions in noble gas, aliphatic hydrocarbon, saturated alicyclic hydrocarbon, halothane hydrocarbon, ether and ketone；

6. the compositions preparing phosphorous copolyester foam according to claim 5, it is characterised in that: the density of described phosphorous copolyester foam is 30-650kg/m³；

Described viscosifier are chain extender or tackifier masterbatch 0.1-30wt% chain extender and 70-99.9wt% vector resin melting mixing obtained；

Described foaming agent is selected from the carbon dioxide in noble gas or nitrogen。

7. the compositions preparing phosphorous copolyester foam according to claim 6, it is characterised in that: the mixture of described chain extender a kind of or they arbitrary proportions in polyfunctional group isoxazoline compound, polyfunctional isocyanate, multi-functional epoxy compound, multifunctional anhydride and polyphosphate compound；

The mixture of described vector resin a kind of or they arbitrary proportions in vistanex, conjugated polyester resin, nylon resin and polycarbonate resin。

8. the compositions preparing phosphorous copolyester foam according to claim 7, it is characterised in that: the mixture of described vector resin a kind of or they arbitrary proportions in acrylic resin, maleic acid graft polypropylene, Merlon and PETG resin。

9. the method that the compositions that phosphorous copolyester foam is prepared in a use as claimed in claim 1 prepares phosphorous copolyester foam, it is characterized in that: comprise the following steps: by the general purpose polyester of formula ratio, reactive phosphonium flame retardant, viscosifier, foaming agent and nucleator are under the melt temperature of general purpose polyester, modifiied by extruder reactive blending, by die extrusion foaming, obtain phosphorous copolyester foam, more this foam is drawn, cuts, namely prepare finished product。

10. the method that the compositions that phosphorous copolyester foam is prepared in a use as claimed in claim 1 prepares phosphorous copolyester foam, it is characterised in that: comprise the following steps: