CN115304742A - 一种无卤阻燃tpu材料及其制备方法 - Google Patents
一种无卤阻燃tpu材料及其制备方法 Download PDFInfo
- Publication number
- CN115304742A CN115304742A CN202210908350.2A CN202210908350A CN115304742A CN 115304742 A CN115304742 A CN 115304742A CN 202210908350 A CN202210908350 A CN 202210908350A CN 115304742 A CN115304742 A CN 115304742A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- halogen
- free flame
- diol
- tpu material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3882—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to oxygen only
- C08G18/3885—Phosphate compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种无卤阻燃TPU材料及其制备方法,其中,一种无卤阻燃TPU材料,包括如下重量百分比的原料:聚合物二元醇45%‑65%,4,4’‑二苯基甲烷二异氰酸酯25%‑35%,小分子二元醇扩链剂1.6%‑10%,含磷、氮元素的小分子二元醇扩链剂2%‑10%,交联剂0.01%‑0.2%,催化剂0.001%‑0.01%,抗氧剂0.1%‑1%,润滑剂0.2%‑2%,无卤阻燃剂3%‑10%。本发明提供的一种无卤阻燃TPU材料,其在阻燃剂添加量少的情况下依然可实现良好的阻燃效果,阻燃效果更优;同时,其中的拉伸强度和断裂伸长率等力学性能相对于纯添加型阻燃剂改性产品更高,这在一定程度上降低了成本,提高了产品附加值,相比于纯添加型阻燃剂改性产品效果更优异。
Description
技术领域
本发明涉及阻燃材料领域,具体涉及一种无卤阻燃TPU材料及其制备方法。
背景技术
热塑性聚氨酯弹性体(TPU)是一种性能优异的环保材料,具有卓越的耐磨性,良好的机械性能,出色的耐高低温性能,广泛应用于电线电缆行业中,但纯TPU极易燃烧,且燃烧过程中伴随着大量的黑烟和熔滴现象,有扩大火灾的风险,这在一定程度上限制了TPU在电线电缆领域的应用。
目前市场上主流的TPU阻燃改性方法主要是采用TPU基料与一定重量百分比的添加型阻燃剂在双螺杆挤出机中熔融共混,挤出造粒干燥后得到改性成品,如专利文献CN106366635A,CN103436005A,CN10674999A,WO2021028999A1,CN107892808A等采用磷氮系无卤阻燃剂复配的方法制备出阻燃TPU复合材料,但这种阻燃改性的方法主要存在着以下问题:
(1)阻燃剂不参与反应,有效阻燃成分不能进入树脂分子链中,同时伴随一定程度的阻燃剂分解,因而导致阻燃效率相对较低;
(2)阻燃剂的添加量相对较大,改性成本较高;
(3)较多阻燃剂的添加导致成品力学性能相对较低,加工不稳定;
(4)较多阻燃剂的添加导致在加工过程中阻燃剂易析出等。
发明内容
因此,本发明要解决的技术问题在于,克服现有技术中的阻燃改性TPU材料需要在较多阻燃剂的添加量下才能获得较好的阻燃效果的问题,本发明提供了将反应型和添加型阻燃改性相结合的一种无卤阻燃TPU材料及其制备方法,使获得的产品即使在较低的阻燃剂添加量下依然具有阻燃等级高的优势。
一种无卤阻燃TPU材料,包括如下重量百分比的原料:
聚合物二元醇(polyol) 45%-65%,
4,4’-二苯基甲烷二异氰酸酯(MDI) 25%-35%,
小分子二元醇扩链剂 1.6%-10%,优选为5%-10%,
含磷、氮元素的小分子二元醇扩链剂 2%-10%,优选为2%-5%,
交联剂 0.01%-0.2%,
催化剂 0.001%-0.01%,
抗氧剂 0.1%-1%,优选为0.2%-0.5%,
润滑剂 0.2%-2%,优选为0.2%-1%,更优选为0.2%-0.5%,
无卤阻燃剂 3%-10%,优选为3%-5%。
所述聚合物二元醇为聚酯二元醇或/和聚醚二元醇;优选的,所述聚合物二元醇包括己二酸系聚酯二元醇、苯甲酸系聚酯二元醇、聚碳酸酯二元醇、聚己内酯二元醇、聚四氢呋喃二元醇、聚环氧丙烷二元醇和聚环氧乙烷二元醇中的至少一种。
所述小分子二元醇扩链剂为1,4-丁二醇(BDO)。
所述含磷、氮元素的小分子二元醇扩链剂的结构式为:
其中,R1和R2均为-CH2-CH2,R3为甲基、乙基、苯基或苯甲基。
所述交联剂为三羟甲基丙烷(TMP)或多异氰酸根预聚物;优选的,多异氰酸根预聚物中异氰酸根的平均官能度为2.5。
所述催化剂为有机锡类催化剂、有机铋类催化剂或钛酸酯类催化剂。
所述无卤阻燃剂为磷酸三苯酯(TPP),叔丁基苯基磷酸二苯酯(BPDP),甲苯磷酸二苯酯(CDP),间苯二酚双磷酸二苯酯(RDP),双份A双磷酸二苯酯(BDP),聚磷酸铵(APP),次磷酸铝(AHP),二乙基次磷酸铝(ADP),三聚氰胺,三聚氰胺聚磷酸盐(MPP),三聚氰胺氰尿酸盐(MCA)中的至少一种;
所述抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(抗氧剂1010),N,N-1,6-亚已基-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰胺(抗氧剂1098),β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯(抗氧剂1076),N,N’-双[β-(3,5-二叔丁基-4-羟基苯基)丙酰](抗氧剂1024),二缩三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯](抗氧剂245),亚磷酸三(2,4-二叔丁基苯基)酯(抗氧剂168),双(2,4-二叔丁基苯酚)季戊四醇二亚磷酸酯(抗氧剂626),二异丙醇醚二亚磷酸二苯酯(THOP)中的至少一种。
所述润滑剂为硬脂酸,硬脂酸盐,硅酮粉,硅酮母粒,乙撑双硬脂酸酰胺,油酸酰胺,乙撑双油酸酰胺,芥酸酰胺,蒙旦酸酯,季戊四醇酯中的至少一种。
本发明还包括0%-5%的助剂。
所述助剂为相容剂、耐水解剂、抗UV助剂、消光助剂、耐磨助剂、惰性填料中的至少一种。
一种无卤阻燃TPU材料的制备方法,包括:
将聚合物二元醇真空脱水确保水分含量低于300ppm,然后将催化剂、抗氧剂、润滑剂投入到聚合物二元醇中搅拌溶解并均匀分散获得预混物;
将4,4’-二苯基甲烷二异氰酸酯,预混物,小分子二元醇扩链剂,含磷、氮元素的小分子二元醇扩链剂混合获得混合物;
将混合物在设置温度为160-260℃,螺杆转速为150-300rpm的条件下反应,反应完成后加入无卤阻燃剂,然后经过挤出造粒、干燥即可。
所述交联剂与聚合物二元醇一起混合形成预混物,或与无卤阻燃剂一起添加到预混物中;
所述制备过程中还包括添加助剂的步骤,所述助剂混合在聚合物二元醇中形成预混物。
本发明技术方案,具有如下优点:
1.本发明提供的一种无卤阻燃TPU材料,其在阻燃剂添加量少的情况下依然可实现良好的阻燃效果,阻燃效果更优。
2.本发明提供的无卤阻燃TPU材料,通过原料优化,其不仅仅能达到更优的阻燃效果;同时,其中的拉伸强度、断裂伸长率等综合力学性能相对于纯添加型阻燃剂改性产品更高,这在一定程度上降低了成本,提高了产品附加值,相比于纯添加型阻燃剂改性产品效果更优异。
3.本发明的制备方法可以制备出80A-65D的无卤阻燃TPU材料,其1.6mm厚度UL阻燃等级V0,拉伸强度≥26MPa,断裂伸长率≥470%,100%模量≥5,300%模量≥10,撕裂强度≥67N/mm,该产品易加工稳定,完全能满足电线电缆护套的使用要求。
具体实施方式
提供下述实施例是为了更好地进一步理解本发明,并不局限于所述最佳实施方式,不对本发明的内容和保护范围构成限制,任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品,均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或条件者,按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规试剂产品。
以下实施例中:
聚四氢呋喃二元醇(PTMEG,BASF,型号PolyTHF1000,分子量1000),聚己二酸丁二醇酯(PBA,厂家浙江华峰,型号PE-4030,分子量2000),聚碳酸酯二醇(PCDL,厂家日本宇部,型号UH200,分子量2000),聚己内酯二醇(PCL,厂家英杰维特Ingevity,型号Capa2201A,分子量2000);
催化剂T9(辛酸亚锡,厂家Evonic,型号Kosmos T9);
交联剂三羟甲基丙烷(TMP,厂家百川化工),交联剂多异氰酸酯预聚物(厂家BASF,型号Lupranate 266);
抗氧剂1010(厂家BASF,型号Irganox 1010),抗氧剂1098(厂家BASF,型号Irganox1098),抗氧剂626(厂家天津利安隆,型号Rianox 626),抗氧剂THOP(厂家青岛杰得佳,型号JADEWIN THOP);
润滑剂乙撑双硬脂酸酰胺(EBS,厂家KLK OLEO,型号PALMOWAX EBS);
1,4-丁二醇(BDO,美克化工);
4,4’-二苯基甲烷二异氰酸酯(MDI,厂家Covestro,型号Desmodur 44C);
含磷小分子二元醇:
Fyrol 6(O,O’-二乙基-N,N-双(2-羟基乙基)氨甲基膦酸酯,厂家ICLIndustrial,型号Fyrol 6),OP550(厂家科莱恩,型号Exolit OP550);
阻燃剂:
甲苯磷酸二苯酯(CDP,厂家浙江万盛股份有限公司,型号WSFR-CDP),间苯二酚双磷酸二苯酯(RDP,厂家浙江万盛股份有限公司,型号WSFR-RDP),双份A双磷酸二苯酯(BDP,厂家浙江万盛股份有限公司,型号WSFR-BDP),叔丁基苯基磷酸二苯酯(BPDP,厂家Lanxess,型号Disflamoll 51092)。
实施例1
一种无卤阻燃TPU材料的制备方法,具体制备过程为:
将聚四氢呋喃二元醇(PTMEG)在100℃条件下真空脱水,确保水分含量低于300ppm。每61.37kg已脱水的PTMEG中,称量0.006kg催化剂T9,0.012kg交联剂TMP,0.25kg抗氧剂1010,0.13kg抗氧剂626,0.24kg润滑剂乙撑双硬脂酸酰胺(EBS)投入到已脱水的PTMEG中搅拌溶解获得预混物。
将62kg的预混物与5kg的BDO、25kg的MDI、3kg的0,0’-二乙基-N,N-双(2-羟基乙基)氨甲基膦酸酯(Fyrol 6)精确计量投入到高速搅拌的预混罐中混合均匀通过浇注机喂入到温度设置为160-260℃,螺杆转速为150rpm的同向双螺杆挤出机,并在挤出机的后端喂料口喂入5kg的阻燃剂甲苯磷酸二苯酯(CDP),然后通过挤出造粒,干燥后得阻燃TPU产品。
实施例2
一种无卤阻燃TPU材料的制备方法,具体制备过程为:
将聚四氢呋喃二元醇(PTMEG)在100℃条件下真空脱水,确保水分含量低于300ppm。每56.41kg已脱水的PTMEG中,称量0.005kg催化剂T9,0.01kg交联剂TMP,0.22kg抗氧剂1098,0.13kg抗氧剂626,0.23kg润滑剂乙撑双硬脂酸酰胺(EBS)投入到已脱水的PTMEG中搅拌溶解获得预混物。
将57kg的预混物与6.7kg的BDO、28.6kg的MDI、3kg的含磷小分子二元醇(OP550)精确计量投入到高速搅拌的预混罐中混合均匀通过浇注机喂入到温度设置为160-260℃,螺杆转速为240rpm的同向双螺杆挤出机,并在挤出机的后端喂料口喂入4.7kg的阻燃剂间苯二酚双磷酸二苯酯(RDP),然后通过挤出造粒,干燥后得阻燃TPU产品。
实施例3
一种无卤阻燃TPU材料的制备方法,具体制备过程为:
将聚己二酸丁二醇酯(PBA)在100℃条件下真空脱水,确保水分含量低于300ppm。每54.44kg已脱水的PBA中,称量0.005kg催化剂T9,0.01kg交联剂TMP,0.22kg抗氧剂1010,0.11kg抗氧剂THOP,0.22kg润滑剂乙撑双硬脂酸酰胺(EBS)投入到已脱水的PTMEG中搅拌溶解获得预混物。
将55kg的预混物与7.5kg的BDO、30.5kg的MDI、2kg的含磷小分子二元醇(OP550)精确计量投入到高速搅拌的预混罐中混合均匀通过浇注机喂入到温度设置为160-260℃,螺杆转速为240rpm的同向双螺杆挤出机,并在挤出机的后端喂料口喂入5kg的阻燃剂双份A双磷酸二苯酯(BDP),然后通过挤出造粒,干燥后得阻燃TPU产品。
实施例4
一种无卤阻燃TPU材料的制备方法,具体制备过程为:
将聚碳酸酯二醇(PCDL)在100℃条件下真空脱水,确保水分含量低于300ppm。每47.11kg已脱水的PCD中,称量0.005kg催化剂T9,0.19kg抗氧剂1010,0.09kg抗氧剂THOP,0.21kg润滑剂乙撑双硬脂酸酰胺(EBS)投入到已脱水的PTMEG中搅拌溶解获得预混物。
将47.6kg的预混物与9.5kg的BDO、34.3kg的MDI、3.8kg的0,0’-二乙基-N,N-双(2-羟基乙基)氨甲基膦酸酯(Fyrol 6)精确计量投入到高速搅拌的预混罐中混合均匀通过浇注机喂入到温度设置为160-260℃,螺杆转速为250rpm的同向双螺杆挤出机,并在挤出机的后端喂料口喂入0.2kg交联剂多异氰酸酯预聚物和4.6kg的阻燃剂叔丁基苯基磷酸二苯酯(BPDP),然后通过挤出造粒,干燥后得阻燃TPU产品。
实施例5
一种无卤阻燃TPU材料的制备方法,具体制备过程为:
将聚己内酯二醇(PCL)在100℃条件下真空脱水,确保水分含量低于300ppm。每58.4kg已脱水的PCL中,称量0.006kg催化剂T9,0.24kg抗氧剂1010,0.12kg抗氧剂THOP,0.24kg润滑剂乙撑双硬脂酸酰胺(EBS)投入到已脱水的PCL中搅拌溶解获得预混物。
将59kg的预混物与5.7kg的BDO、27.6kg的MDI、2.9kg的含磷小分子二元醇(OP550)精确计量投入到高速搅拌的预混罐中混合均匀通过浇注机喂入到温度设置为160-260℃,螺杆转速为280rpm的同向双螺杆挤出机,并在挤出机的后端喂料口喂入0.2kg交联剂多异氰酸酯预聚物和4.6kg的阻燃剂甲苯磷酸二苯酯(CDP),然后通过挤出造粒,干燥后得阻燃TPU产品。
对比例1
将聚己二酸丁二醇酯(PBA)在100℃条件下真空脱水,确保水分含量低于300ppm。每54.44kg已脱水的PBA中,称量0.005kg催化剂T9,0.01kg交联剂TMP,0.22kg抗氧剂1010,0.11kg抗氧剂THOP,0.22kg润滑剂乙撑双硬脂酸酰胺(EBS)投入到已脱水的PBA中搅拌溶解获得预混物。
将55kg的预混物与11.25kg的BDO、37.85kg的MDI精确计量投入到高速搅拌的预混罐中混合均匀通过浇注机喂入到温度设置为160-260℃,螺杆转速为240rpm的同向双螺杆挤出机,水下切粒干燥得聚酯型TPU基料粒子。
将85kg上述方法制备的聚酯型TPU基料粒子(佳化化学JH-A2195)于100℃条件下干燥3h,准确称取15kg的无卤阻燃剂(质量比为1:1的次磷酸铝和三聚氰胺聚磷酸盐的复配物)于100℃条件下干燥10h,然后与0.4kg的抗氧剂(1010),0.3kg的润滑剂(EBS)在高速混合机中混合均匀,并投入到双螺杆挤出机中于200℃,转速为200rpm的条件下共混挤出造粒干燥后得成品。
对比例2
将聚四氢呋喃二元醇(PTMEG)在100℃条件下真空脱水,确保水分含量低于300ppm。每61.37kg已脱水的PTMEG中,称量0.006kg催化剂T9,0.012kg交联剂TMP,0.25kg抗氧剂1010,0.13kg抗氧剂626,0.24kg润滑剂乙撑双硬脂酸酰胺(EBS)投入到已脱水的PTMEG中搅拌溶解获得预混物。
将62kg的预混物与6.67kg的BDO,33.71kg的MDI精确计量投入到高速搅拌的预混罐中混合均匀通过浇注机喂入到温度设置为160-260℃,螺杆转速为150rpm的同向双螺杆挤出机,水下切粒干燥得聚四氢呋喃型TPU基料粒子。
将70kg上述方法制备的聚四氢呋喃型TPU基料粒子(佳化化学,JH-B1285)于100℃条件下干燥3h,准确称取30kg的无卤阻燃剂(质量比为1:1:1的有机次磷酸铝与三聚氰胺氰尿酸盐、三聚氰胺聚磷酸盐的复配物)于100℃条件下干燥10h,然后同时与0.4kg的抗氧剂1010,0.3kg的润滑剂EBS在高速混合机中混合均匀,投入到双螺杆挤出机中于200℃,转速为200rpm的条件下共混挤出造粒干燥后得成品。
试验例
采用上述实施例和对比例制备得到的样品进行硬度、拉伸强度、断裂伸长率、100%模量、300%模量、撕裂强度、UL阻燃等级检测,其中,各测试项目采用以下标准进行检测:
硬度测试标准ASTM D2240,
拉伸强度测试标准ASTM D412,
断裂伸长率测试标准ASTM D412,
100%模量测试标准ASTM D412,
300%模量测试标准ASTM D412,
撕裂强度测试标准ASTM D624,
阻燃等级测试标准UL94。
采用上述检测手段测试得到的结果如表1所示。
表1
通过以上数据对比标明,采用本发明制备的TPU产品在阻燃剂添加量更少的情况下可实现良好的阻燃效果,1.6mm厚度UL阻燃等级可以达到V0,阻燃效果显著。
同时,其中的拉伸强度、断裂伸长率和撕裂强度等力学性能相对于纯添加型阻燃剂改性产品而言,本发明的综合力学性能更高,这在一定程度上降低了成本,提高了产品附加值。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (10)
2.根据权利要求1所述的一种无卤阻燃TPU材料,其特征在于,所述聚合物二元醇为聚酯二元醇或/和聚醚二元醇;优选的,所述聚合物二元醇包括己二酸系聚酯二元醇、苯甲酸系聚酯二元醇、聚碳酸酯二元醇、聚己内酯二元醇、聚四氢呋喃二元醇、聚环氧丙烷二元醇和聚环氧乙烷二元醇中的至少一种。
3.根据权利要求1或2所述的一种无卤阻燃TPU材料,其特征在于,所述小分子二元醇扩链剂为1,4-丁二醇。
5.根据权利要求1-4任一项所述的一种无卤阻燃TPU材料,其特征在于,所述交联剂为三羟甲基丙烷或多异氰酸根预聚物。
6.根据权利要求1-5任一项所述的一种无卤阻燃TPU材料,其特征在于,所述无卤阻燃剂为磷酸三苯酯,叔丁基苯基磷酸二苯酯,甲苯磷酸二苯酯,间苯二酚双磷酸二苯酯,双份A双磷酸二苯酯,聚磷酸铵,次磷酸铝,二乙基次磷酸铝,三聚氰胺,三聚氰胺聚磷酸盐,三聚氰胺氰尿酸盐中的至少一种。
7.根据权利要求1-6任一项所述的一种无卤阻燃TPU材料,其特征在于,所述催化剂为有机锡类催化剂、有机铋类催化剂或钛酸酯类催化剂;
所述抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯,N,N-1,6-亚已基-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰胺,β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯,N,N’-双[β-(3,5-二叔丁基-4-羟基苯基)丙酰],二缩三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯],亚磷酸三(2,4-二叔丁基苯基)酯,双(2,4-二叔丁基苯酚)季戊四醇二亚磷酸酯,二异丙醇醚二亚磷酸二苯酯中的至少一种;
所述润滑剂为硬脂酸,硬脂酸盐,硅酮粉,硅酮母粒,乙撑双硬脂酸酰胺,油酸酰胺,乙撑双油酸酰胺,芥酸酰胺,蒙旦酸酯,季戊四醇酯中的至少一种。
8.根据权利要求1-7任一项所述的一种无卤阻燃TPU材料,其特征在于,还包括0%-5%的助剂;优选的,所述助剂为相容剂、耐水解剂、抗UV助剂、消光助剂、耐磨助剂、惰性填料中的至少一种。
9.权利要求1-8任一项所述的一种无卤阻燃TPU材料的制备方法,其特征在于,包括:
将聚合物二元醇真空脱水确保水分含量低于300ppm,然后将催化剂、抗氧剂、润滑剂投入到聚合物二元醇中搅拌溶解并均匀分散获得预混物;
将4,4’-二苯基甲烷二异氰酸酯,预混物,小分子二元醇扩链剂,含磷、氮元素的小分子二元醇扩链剂混合获得混合物;
将混合物在设置温度为160-260℃,双螺杆转速为150-300rpm的条件下反应,反应完成后加入无卤阻燃剂,然后经过挤出造粒、干燥即可。
10.根据权利要求9所述的制备方法,其特征在于,所述交联剂与聚合物二元醇一起混合形成预混物,或与无卤阻燃剂一起添加到预混物中;
所述制备过程中还包括添加助剂的步骤,所述助剂混合在聚合物二元醇中形成预混物。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210908350.2A CN115304742A (zh) | 2022-07-29 | 2022-07-29 | 一种无卤阻燃tpu材料及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210908350.2A CN115304742A (zh) | 2022-07-29 | 2022-07-29 | 一种无卤阻燃tpu材料及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115304742A true CN115304742A (zh) | 2022-11-08 |
Family
ID=83858169
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210908350.2A Pending CN115304742A (zh) | 2022-07-29 | 2022-07-29 | 一种无卤阻燃tpu材料及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115304742A (zh) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1495214A (zh) * | 2002-08-21 | 2004-05-12 | 具有自熄性的可热塑加工的聚氨酯及其制备方法与应用 | |
CN109666126A (zh) * | 2018-12-24 | 2019-04-23 | 山东诺威聚氨酯股份有限公司 | 本质阻燃热塑性聚氨酯弹性体材料及其制备方法 |
-
2022
- 2022-07-29 CN CN202210908350.2A patent/CN115304742A/zh active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1495214A (zh) * | 2002-08-21 | 2004-05-12 | 具有自熄性的可热塑加工的聚氨酯及其制备方法与应用 | |
CN109666126A (zh) * | 2018-12-24 | 2019-04-23 | 山东诺威聚氨酯股份有限公司 | 本质阻燃热塑性聚氨酯弹性体材料及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102260367B (zh) | 一种热塑性聚氨酯弹性体及其制备方法 | |
TWI491672B (zh) | 非鹵素難燃劑熱塑性聚胺基甲酸酯 | |
KR101703377B1 (ko) | 할로겐-무함유 난연제 조성물 | |
KR102259248B1 (ko) | 할로겐-비함유 방염 tpu | |
CN101580574A (zh) | 阻燃热塑性聚氨酯弹性体的制备方法 | |
KR102267207B1 (ko) | 폴리에스테르계 수지 조성물, 및 상기 폴리에스테르계 수지 조성물을 이용한 성형품 | |
TW200938576A (en) | Halogen-free flame retardant thermoplastic polyurethanes | |
TWI500694B (zh) | 可熔融加工之共聚醚醯胺彈性體及其製法 | |
CN108003605B (zh) | 无卤阻燃tpu包胶材料及其制备方法 | |
CN104140559A (zh) | 环状磷腈化合物作为阻燃剂在制备树脂中的应用 | |
EP3230355B1 (en) | Halogen-free flame-retardant composition | |
KR20070055886A (ko) | 비할로겐 난연 열가소성 폴리우레탄 복합 수지 조성물 | |
WO2008045853A1 (en) | Thermoplastic polyurethanes containing a salt of zirconium phosphate | |
CN101570632A (zh) | 一种无卤阻燃热塑性聚氨酯塑料及其制备方法 | |
CN110951043A (zh) | 高效无卤阻燃tpu材料及其制备方法 | |
JP2014084435A (ja) | 難燃性樹脂組成物 | |
JP2005534725A (ja) | 燃焼中の発煙性が低い熱可塑性ポリウレタン | |
KR101407251B1 (ko) | 비할로겐 난연 열가소성 폴리우레탄 복합수지 조성물 | |
CN115304742A (zh) | 一种无卤阻燃tpu材料及其制备方法 | |
CN115260739B (zh) | 一种tpu阻燃母粒、tpu薄膜及其制备方法和应用 | |
CN116601226A (zh) | 阻燃热塑性聚氨酯 | |
CN111253731B (zh) | 一种无卤阻燃热塑性聚氨酯弹性体及其制备方法 | |
CN116194519A (zh) | 阻燃热塑性聚氨酯 | |
CN110144112B (zh) | 无卤电缆料及其制备方法和包含该无卤电缆料的电缆 | |
CN112955428A (zh) | 聚碳化二亚胺化合物、以及使用其的聚酯树脂组合物和聚酯树脂改性剂 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |