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碳酸二苯酯(DPC,Diphenyl carbonate,Phenyl carbonate,CAS登录号:102-09-0)是一种多功能化工中间体,不仅广泛用于溶剂、增塑剂、医药、农药等领域,而且是合成聚碳酸酯(PC)的关键原料。
PC是一种性能优良、应用广泛的热塑性通用工程塑料,近年来国内外消费量快速增长。我国高质量的PC几乎全部依赖进口,2005年进口量高达73万吨,预计未来5-10年其消费量将以10-15%的速度增加。
目前碳酸二苯酯的生产以光气法为主,由于光气有剧毒,因此该法存在严重的环境安全问题;酯交换法可在150~250℃、常压或减压条件下进行,但由于反应平衡常数较小,且反应速率很低,不利于产物的生成,同时降低了催化剂的负荷;氧化羰化法与其他方法相比具有无污水、不需溶剂、无有毒盐生成、工艺相对简单、原料价廉易得等优点,但是由于苯酚具有易被氧化的特殊性质,使得此方法的应用受到限制。同时,由于催化剂昂贵、转化效率不高以及DPC 产率低等因素,致使氧化羰基化法合成DPC 的工艺迄今尚未见工业化报道;至于酯交换脱羰反应,此法目前仍处研究阶段,离工业化还有相当的距离。
除以上几种制备方法外,尿素酚解法跟上述几种方法相比具有不使用光气、原料价格低廉、工艺简单以及产品收率相对较高等特点而受到广泛关注。
以尿素酚解是制备碳酸二苯酯最经济和安全的路线,无论是从原料成本、环境友好生产还是反应产物纯度,该法都具有最大的优势,该法在尿素生产厂联产更有优势,它是碳酸二苯酯今后工业生产的发展方向。目前,通过尿素酚解制备碳酸二苯酯还没有实现工业化生产,主要原因是催化剂和合成最佳工艺没有优化。 尿素是一种大宗廉价的农用化学品(约2000元/吨),将其在催化剂和一定工艺条件下醇解合成碳酸酯类化合物,特别是酚解制备碳酸二苯酯等有非常好的应用前景。申请者已对尿素酚解合成碳酸二苯酯等进行了系统研究,取得了一些结果。从研究结果来看,在研究新型高效催化剂的同时,还应注意合成反应的工艺过程开发和技术集成,使尿素酚解工艺快速实现产业化,对我国化肥行业产品结构调整、技术进步和化工清洁生产以及经济发展做出贡献。 碳酸二苯酯是制备聚碳酸酯等的主要原料,粗产物经减压精馏后可达到聚碳级要求。
现有报道的主要合成方法有1)光气法,2)固体光气法,3)碳酸二甲酯交换法,4)草酸二甲酯交换去羰法,5)CO催化氧化法,6)尿素分解法。
尿素酚解法跟上述几种方法相比具有不使用光气、原料价格低廉、工艺简单以及产品收率相对较高等特点而受到广泛关注。Mizukami 等人报道通过以下过程实现尿素合成碳酸二苯酯:(a)尿素和脂肪族醇反应形成烷基酯;(b)烷基酯与烃基芳香化合物进行酯交换反应;(c)未反应的羧酸酯进行取代反应形成碳酸二苯酯。其中步骤(b)和(c)产生的脂肪族醇可回到(a)步骤循环使用。我校谢庆兰教授曾以四丁基二锡氧烷为催化剂,通过尿素的醇解反应合成碳酸高碳醇酯的最大收率达到86.7 %。
铜谷正晴和大川隆报道合成二芳基碳酸酯的方法克服了以往反应收率低、原料和催化剂价格昂贵的缺点,用氧化锌作为催化剂,在160℃、17MPa (表压)下反应1h 后经过2h 升温升压到200℃、111MPa (表压)制得的二芳基碳酸酯的收率达到了92.8 %。用其它催化剂如氧化镁、铝粉、氯化钙、四丁基钛等为催化剂时,相应的二芳基碳酸酯的收率都达到了80 %以上。伊藤光则报道用尿素和苯酚类的化合物反应合成芳香族类的碳酸二酯类化合物, 利用LiAlH4,LiBH4,NaBH4,LiBEt3H,Et2CuLi,LiOH 作为催化剂,其中LiAlH4 的催化效果最好,几种碳酸酯的收率都在10 %左右,其它的催化剂都低于10 %。
合成技术路线:
 H2NCONH2 + 2 C6H5OH = C6H5OCO2C6H5 + 2 NH3 反应进行的关键是选择合适的催化剂。 随着碳酸二苯酯的市场需求不断增加,低成本和洁净化工业生产过程制备碳酸二苯酯的方法和工艺有广泛的应用前景,也能和大型苯酚丙酮项目相配套,提高其主要产品的附加值和市场销路。
在釜式反应器或固定床催化反应器中实现尿素苯酚反应制备碳酸二苯酯,达到的技术指标为: 1)尿素的转化率为100%; 2)目标产物的选择性≥75%; 3)釜式反应的反应时间不超过8小时; 4)催化剂吨原料成本不超过15万; 5)酚和尿素总单耗≤2吨/吨产品,精馏分离出的产品纯度≥99%。

为维护中技网平台交易秩序,保护技术需求方合法权益,本人(本单位)特做出以下承诺和声明:
一、本人(本单位)专利技术是经国家知识产权局审定认可,并取得了该项知识产权的专利证书,信息真实,技术可靠,无知识产权纠纷。
二、本人(本单位)愿意根据《中华人民共和国合同法》、《中华人民共和国专利法》、《中华人民共和国知识产权保护法》和《中华人民共和国促进科技成果转化法》以及中技网平台制定的技术转移交易规则和制度进行规范交易,自觉维护技术转移网络交易秩序。
三、如本人(本单位)在技术转移转化过程中有严重违规违约行为,给平台和交易相对方造成经济或财产损失,本人(本单位)愿意承担相应责任。

For maintenance or web platform trading order, protect the legal rights of the technical demand (units), make the following commitment and declaration:

1I (unit) patent technology is approved by the state intellectual property office and obtained the patent certificate of this intellectual property, the information is true, the technology is reliable, and there is no intellectual property dispute.

2, I (unit) willing to according to the law of the People's Republic of China contract law ", "patent law of the People's Republic of China, the intellectual property rights of the People's Republic of China protects a law" and "promote the conversion of scientific and technological achievements of the People's Republic of China" and wowed net platform to develop the trading rules and the system of technology transfer of regulate transactions, consciously safeguard the order of the technology transfer network transactions.

3.If I (unit) in the process of the transformation of technology transfer has seriously violated the breach, to economic or property damage caused by platform and trade each other, I (the unit) are willing to bear the corresponding legal responsibility.

交易规则说明

1、转让方在委托服务商转让期间,首先要认真阅读中技网会员协议和技术商品交易规则,其次要了解中技网有关收费标准,清楚应当遵守的相关权利和义务

2、购买方在中技网平台上认定购买某一项技术商品前,需要按照规定向中技网平台支付定金(完成意向性购买),但知识产权归属以及何时能够使用该项知识产权,视买卖双方协商确定后才能够使用,在此之前,建议您不要使用或侵犯他人的知识产权。

3、本网站对上传在首页各版块展示出售的技术产品实行有偿服务原则,对拟出售的专利技术产品交易价格以及市场前景,中技网将根据财政部无形资产评估有关标准和规定给予客观、公正的评价,具体收费标准请咨询客服人员。

1, the assignor in commissioned services during the transfer, the first thing to read or member agreement and the technical commodity trading rules, second to understand relevant charge standard or network platform, which shall comply with the relevant rights and obligations.

2, the purchaser on or network platform, decided to buy a certain technology products before, need to pay a deposit in accordance with the relevant provisions to or net platform (complete intentional purchase), but the intellectual property ownership and when to be able to use the intellectual property rights, after the negotiation between the buyers and sellers can use, before that, it is recommended that you do not use or infringe others' intellectual property.

3, this website to upload on the home page of each section shows the sale of products shall be paid for the service principle, to plans to sell the patent technology of the product market price and the market prospects, or network will according to the ministry of finance of intangible assets evaluation of relevant standards and regulations to give an objective and fair evaluation, specific charge standard, please consult customer service staff.

交易流程

根据中技网交易规则,技术买卖双方应当遵循友好、自愿和有偿原则进行交易,为此,请技术买卖双方应当遵循中技网制定的交易流程进行有序买卖。
一、买方确定购买意向→支付定金→签订意向性购买协议→买卖双方签订正式协议→买方付款 →办理技术转移交割手续→资金结算→交易完成→退还定金。

二、卖方提交信息资料→上传有效证明文件→平台审核→与平台签订相关协议和信用保证金协议→缴纳信用保证金→平台发布出让信息→确定买家→签订协议→出让技术→资金结算→交易完成→退还信用保证金。

    According to trading rules or network technology between buyer and seller shall follow the principle of friendly, voluntary and paid, for this, please technology between buyer and seller shall follow the wowed the orderly sale network of trading process.

One, the buyer to determine the purchase intentions to pay the deposit, intentional purchase agreement to sign a formal agreement between the seller and the buyer, the buyer's payment to delivery technology transfer formalities, fund settlement - deal - return deposit.

Second, the seller submit information to upload valid documents to review platform, and platform signed the relevant agreement and credit margin agreements to pay credit deposit, platform release transfer information to determine the buyer, signed an agreement to transfer technology, funds and settlements - deal - the refund credit deposit

重要提示

1、技术转让方请务必遵守《中华人民共和国合同法》、《中华人民共和国专利法》、《中华人民共和国知识产权法》、《中华人民共和国促进科技成果转化法》等相关法律法规,诚实守信,不得伪造或提供虚假技术信息。

2、技术购买方在决定购买技术商品前,首先要了解中技网的有关交易流程和技术转让方的详细信息,在购买过程中对有关技术信息产生疑问或不清楚的地方,请随时与技术信息发布单位取得联系。

3、中技网作为市场化运作的专业技术买卖服务平台,由中国技术市场协会主办,是国内权威的专业技术交易分类信息网,专业、专注、权威,面向国内外发布技术转让和技术需求项目信息,服务周到,信誉第一,交易规范,请客户认准中技网官方网址,切勿上当受骗。

1, technology transferor please be sure to abide by the law of the People's Republic of China contract law ", "patent law of the People's Republic of China" and "intellectual property law of the People's Republic of China", "promote the conversion of scientific and technological achievements of the People's Republic of China" and other relevant laws and regulations, the honest code of honor, are not allowed to fake or providing false information technology.

2 the purchaser prior to the decision to buy technology goods, technology, the first thing to understand the assignor or network related transaction process and technology of detailed information, in the process of buying to doubt the related technical information or unclear, please feel free to get in touch with technical information release unit.

3, or as a market-oriented operation of professional technology trading service platform, sponsored by the China technology market association, is the domestic authority of professional technology trading classified information network, professional, dedicated, authority, and the release technology transfer and technology at home and abroad demand project information, service, credit first, trade specification, please customers look or net official web site, please do not be deceived.

郑重声明

  会员在服务期内私自线下与相对交易方进行交易,由当事人自行承担法律后果,所产生的经济或知识产权纠纷中技网不承担任何法律责任。

Membership in the service period to offline, transacting business with relatively by the parties to bear the legal consequences, economic or intellectual property rights disputes or generated by the network does not assume any legal liability.

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