Under external mechanical forces, some polymers can undergo chemical reactions due to their special groups; such polymers are called mechano-responsive polymers.

There are three compounds **1**, **2**, **3**, **4**, and their structures are as follows:

**1**:

<MultiModal>![C(CCCO)CCC1C2=C(C=CC=C2)C3(CCCCCCO)C1C3(Cl)Cl](/media/uploads/f00533ca-26ec-4fe7-8cd2-a5315fa2925c.png)</MultiModal>

**2**:
<MultiModal>![C=C(C)C(=O)OCCOC(=O)C(=C)C
](/media/uploads/97c6be0e-7220-4c7b-9d24-0bfcb848c36e.png)</MultiModal>

**3**:

<MultiModal>![C=C(C)C(=O)OCCCCCCC1C2=C(C=CC=C2)C3(CCCCCCOC(=O)C(=C)C)C1C3(Cl)Cl](/media/uploads/af373aa8-e63c-4ef9-b858-cbb1c626f932.png)</MultiModal>

**4**:

<MultiModal>![CCCCC(C1=CC(N=C(N1[H])NC(NCCOCCOCCOCCOC2=C3C=CC=C(OCCOCCOCCOCCNC(NC4=NC(C=C(N4[H])C(CCCC)CC)=O)=O)C3=CC=C2)=O)=O)CC](/media/uploads/c93a4c69-52e0-46dc-b866-301b63fd7438.png)</MultiModal>

Known: Heating **1** at 50°C for 24h will release HCl to obtain an oily liquid; methyl acrylate is polymerized with benzoyl peroxide as an initiator. If only a small amount of **1** $( \sim 5 \% )$ and **2**$ ( \sim 5 \% )$ are mixed in the system, polymer **A** is obtained; if only a small amount of **3**$ ( \sim 5 \% )$ is mixed in the system, polymer **B** is obtained. Experiments show that **A, B** can release HCl when pressurized, but the amount is different; **4** exists as a cyclic monomer in the solid state, and when it is dissolved in chloroform, when the concentration exceeds a certain value, the viscosity of the solution increases sharply with the concentration. Please select the correct option from the following.
在外界的机械力下，有些聚合物因其具有的特殊基团而可发生化学反应；这样的聚合物被称为机械响应聚合物。

现有三种化合物**1**、**2**、**3**、**4**，它们的结构分别为：

**1**：

<MultiModal>![C(CCCO)CCC1C2=C(C=CC=C2)C3(CCCCCCO)C1C3(Cl)Cl](/media/uploads/f00533ca-26ec-4fe7-8cd2-a5315fa2925c.png)</MultiModal>

**2**：
<MultiModal>![C=C(C)C(=O)OCCOC(=O)C(=C)C
](/media/uploads/97c6be0e-7220-4c7b-9d24-0bfcb848c36e.png)</MultiModal>

**3**：

<MultiModal>![C=C(C)C(=O)OCCCCCCC1C2=C(C=CC=C2)C3(CCCCCCOC(=O)C(=C)C)C1C3(Cl)Cl](/media/uploads/af373aa8-e63c-4ef9-b858-cbb1c626f932.png)</MultiModal>

**4**：

<MultiModal>![CCCCC(C1=CC(N=C(N1[H])NC(NCCOCCOCCOCCOC2=C3C=CC=C(OCCOCCOCCOCCNC(NC4=NC(C=C(N4[H])C(CCCC)CC)=O)=O)C3=CC=C2)=O)=O)CC](/media/uploads/c93a4c69-52e0-46dc-b866-301b63fd7438.png)</MultiModal>

已知：**1**在50℃下加热24h会放出HCl得到油状液体；以过氧化苯甲酰为引发剂引发丙烯酸甲酯聚合，若体系中只混有少量的 **1** $( \sim 5 \% )$ 和**2**$ ( \sim 5 \% )$ ，则得到聚合物**A**；若体系中只混有少量的 **3**$ ( \sim 5 \% )$ ，则得到聚合物**B** 。实验表明，**A，B**加压时均可放出HCI但量不同；**4**在固态时以环状单体形式存在，而当其溶解在氯仿中后，当浓度超过某一值时，溶液的粘度随浓度急剧上升。请选择下列选项中正确的一项。
The stoichiometric ratio of HCl produced by the complete reaction of heating **1** to the resulting product molecules is 2:1.
The aromatic system present in the product molecule obtained by heating **1** contains 6 π electrons.
**A** has a covalently cross-linked network structure while **B** does not.
Under the same pressure, an equal amount of **A** releases more HCl than **B**.
In solid **4**, there are no hydrogen bonds among the non-covalent interactions within the molecule.
The reason for the increase in viscosity of the chloroform solution of **4** with increasing concentration is the formation of one-dimensional supramolecular polymers by **4** molecules, mainly relying on hydrogen bonds rather than covalent reactions, with 5 intermolecular hydrogen bonds that can form between every two monomers.
加热**1**完全反应产生的HCl与得到的产物分子化学计量比是2:1
加热**1**得到的产物分子中存在的芳香体系含有10个π电子
**A**具有共价交联网状结构而**B**不具有
相同压力下，等量**A**释放出的HCl多于**B**
固态**4**分子内的非共价相互作用不存在氢键
**4**的氯仿溶液粘度随浓度增加的原因是**4**分子间形成了一维超分子聚合物，主要依靠氢键而非共价反应，每两个单体间可以形成5根分子间氢键
From the problem statement, heating **1** releases HCl and yields an oily liquid. Since **1** contains two chlorine atoms, it can produce at most two molecules of HCl. After releasing the first molecule of HCl, a stable naphthalene ring system can be formed in the product:

<MultiModal>![OCCCCCCC(C=C1Cl)=C2C(C=CC=C2)=C1CCCCCCO](/media/uploads/9da643c5-8add-4fe4-ad97-97b9bce380b1.png)</MultiModal>

The mechanism of this process is that halogenated cyclopropanes undergo rearrangement under heating conditions to produce allylic halogenated products, which then rapidly aromatize to form a naphthalene ring, releasing one molecule of HCl under heating conditions.

<MultiModal>![机理为多步反应，ClC1(Cl)C2C(CCCCCCO)C3=CC=CC=C3C21CCCCCCO>>ClC1=C(CCCCCCO)C2=CC=CC=C2C(CCCCCCO)[CH+]1.[Cl-]，ClC1=C(CCCCCCO)C2=CC=CC=C2C(CCCCCCO)[CH+]1.[Cl-]>>ClC1=C(CCCCCCO)C2=CC=CC=C2C(CCCCCCO)C1Cl，ClC1=C(CCCCCCO)C2=CC=CC=C2C(CCCCCCO)C1Cl>>ClC1=C(CCCCCCO)C2=CC=CC=C2C(CCCCCCO)=C1，在加热条件下首先高张力的三元环开环，离去一分子氯离子，形成烯丙基正离子，随后离子对反应，产生烯丙基氯代物，最后在芳构化的驱动下离去一分子HCl形成萘环](/media/uploads/e9923800-fd44-49d5-9e1d-f26cbbda1ead.png)</MultiModal>

If the second molecule of HCl continues to be released, the degree of unsaturation of the system will be too high, and the activation energy provided at 50°C is insufficient to allow the Cl attached to the $sp^2$ carbon to depart. Therefore, the stoichiometric ratio of HCl produced by the complete reaction of **1** to the product molecule is 1:1.

<Checkpoint>[释放一分子HCl得到稳定的萘环，第二分子HCl的释放很困难，因此比例为1:1，选项A错误](1)</Checkpoint>

The aromatic system contained in the product is a naphthalene ring, which has 10 π electrons.

<Checkpoint>[由于产物中有萘环，因此有10个π电子，选项B正确](1)</Checkpoint>

Polymer **A** contains approximately 5% of **1** and 5% of **2**. The average functionality of the polymer is calculated as: (0.9×2+0.05×4)÷0.95=2.1. Polymer **B** contains approximately 5% of **3**. The average functionality of the polymer is calculated as: (0.95×2+0.05×4)÷1=2.1, both of which are greater than 2, and can form a covalently cross-linked network structure.

<Checkpoint>[聚合物**A**与**B**的平均官能度均大于2，均可形成网状结构，选项C错误](1)</Checkpoint>

Since **1** cannot be inserted into the polymer network in a covalent manner, it can only be dispersed between the networks; while **3** can participate in the polymerization and be inserted into the polymer network, so B is more sensitive to pressure, and can produce more HCl under the same pressure.

<Checkpoint>[A中压力敏感基团分布在聚合物网络间而B中压力敏感基团参与聚合物网络形成，对压力响应更敏感，可释放更多HCl，选项D错误](1)</Checkpoint>

**4** forms a supramolecular polymer through intermolecular hydrogen bonds. In the solid-state monomer, intramolecular hydrogen bonds are formed instead of intermolecular hydrogen bonds to avoid polymerization.

<MultiModal>![单体两端的脲基与4-嘧啶酮形成分子内氢键，其中脲的两个氨基氢作为给体，4-嘧啶酮的氧和3号位的氮作为受体；4-嘧啶酮1号位氮的氢作为给体，脲的羰基氧作为受体，中心的萘环同时与两端的4-嘧啶酮存在π-π相互作用](/media/uploads/cb1a1a03-3de9-4f15-bf44-0bdd32f25871.png)</MultiModal>

<MultiModal>![更清晰的展示出脲与4-嘧啶酮形成的氢键](/media/uploads/99bfb7c2-9f06-45f5-a0e3-24cc8df04945.png)</MultiModal>

<Checkpoint>[固态单体中同时存在氢键和π-π相互作用，选项E错误](1)</Checkpoint>

After **4** is dissolved in chloroform, it can form a supramolecular polymer through hydrogen bonds. Under these conditions, the carbonyl group of urea will form an intramolecular six-membered ring hydrogen bond with the N-H of 4-pyrimidinone. The remaining two hydrogen bond donors and two hydrogen bond acceptors can form 4 hydrogen bonds between two monomers.

<MultiModal>![图中展示出组装形成超分子聚合物时，分子间形成4根氢键，给体为脲的两个氨基氢，受体为4-嘧啶酮的氧和3号位氮；分子内形成一根氢键，给体为4-嘧啶酮1号位氮上的氢，受体为脲的羰基氧](/media/uploads/7949feff-c59a-4cf3-bb02-29108df457f0.png)</MultiModal>

<Checkpoint>[两个单体间形成4根分子间氢键，选项F错误](1)</Checkpoint>
从题干得知，加热**1**释放出HCl并得到油状液体，而**1**中有两个氯，因此最多可产生两分子HCl，在释放出第一分子HCl后，产物中可以形成稳定的萘环体系：

<MultiModal>![OCCCCCCC(C=C1Cl)=C2C(C=CC=C2)=C1CCCCCCO](/media/uploads/9da643c5-8add-4fe4-ad97-97b9bce380b1.png)</MultiModal>

这一过程的机理是，卤代环丙烷在加热条件下会发生重排，产生烯丙位卤代的产物，随后在加热条件下迅速芳构化生成萘环释放一分子HCl。

<MultiModal>![机理为多步反应，ClC1(Cl)C2C(CCCCCCO)C3=CC=CC=C3C21CCCCCCO>>ClC1=C(CCCCCCO)C2=CC=CC=C2C(CCCCCCO)[CH+]1.[Cl-]，ClC1=C(CCCCCCO)C2=CC=CC=C2C(CCCCCCO)[CH+]1.[Cl-]>>ClC1=C(CCCCCCO)C2=CC=CC=C2C(CCCCCCO)C1Cl，ClC1=C(CCCCCCO)C2=CC=CC=C2C(CCCCCCO)C1Cl>>ClC1=C(CCCCCCO)C2=CC=CC=C2C(CCCCCCO)=C1，在加热条件下首先高张力的三元环开环，离去一分子氯离子，形成烯丙基正离子，随后离子对反应，产生烯丙基氯代物，最后在芳构化的驱动下离去一分子HCl形成萘环](/media/uploads/e9923800-fd44-49d5-9e1d-f26cbbda1ead.png)</MultiModal>

若继续释放第二分子HCl，则体系不饱和度过高，50℃下提供的活化能不足以使连接在$sp^2$碳上的Cl离去。因此**1**完全反应产生的HCl与产物分子的化学计量比为1:1。

<Checkpoint>[释放一分子HCl得到稳定的萘环，第二分子HCl的释放很困难，因此比例为1:1，选项A错误](1)</Checkpoint>

产物中含有的芳香体系为萘环，具有10个π电子。

<Checkpoint>[由于产物中有萘环，因此有10个π电子，选项B正确](1)</Checkpoint>

聚合物**A**中混有约5%的**1**和5%的**2**，计算该聚合物的平均官能度为：(0.9×2+0.05×4)÷0.95=2.1；聚合物**B**中混有约5%的**3**，计算该聚合物的平均官能度为：(0.95×2+0.05×4)÷1=2.1，均大于2，可以形成共价交联网状结构。

<Checkpoint>[聚合物**A**与**B**的平均官能度均大于2，均可形成网状结构，选项C错误](1)</Checkpoint>

由于**1**无法通过共价的方式插入聚合网络中，只能分散在网络间；而**3**可以参与聚合插入到聚合网络中，因此B对压力的响应更敏感，相同压力下可以产生更多的HCl。

<Checkpoint>[A中压力敏感基团分布在聚合物网络间而B中压力敏感基团参与聚合物网络形成，对压力响应更敏感，可释放更多HCl，选项D错误](1)</Checkpoint>

**4**通过分子间氢键连接形成超分子聚合物，在固态单体时，形成分子内氢键而非分子间氢键从而避免聚合。

<MultiModal>![单体两端的脲基与4-嘧啶酮形成分子内氢键，其中脲的两个氨基氢作为给体，4-嘧啶酮的氧和3号位的氮作为受体；4-嘧啶酮1号位氮的氢作为给体，脲的羰基氧作为受体，中心的萘环同时与两端的4-嘧啶酮存在π-π相互作用](/media/uploads/cb1a1a03-3de9-4f15-bf44-0bdd32f25871.png)</MultiModal>

<MultiModal>![更清晰的展示出脲与4-嘧啶酮形成的氢键](/media/uploads/99bfb7c2-9f06-45f5-a0e3-24cc8df04945.png)</MultiModal>

<Checkpoint>[固态单体中同时存在氢键和π-π相互作用，选项E错误](1)</Checkpoint>

**4**溶解在氯仿中后，可以通过氢键连接形成超分子聚合物，在该条件下，脲的羰基会与4-嘧啶酮的N-H形成一个分子内六元环氢键，剩余两个氢键给体和两个氢键受体，可在两个单体间形成4根氢键

<MultiModal>![图中展示出组装形成超分子聚合物时，分子间形成4根氢键，给体为脲的两个氨基氢，受体为4-嘧啶酮的氧和3号位氮；分子内形成一根氢键，给体为4-嘧啶酮1号位氮上的氢，受体为脲的羰基氧](/media/uploads/7949feff-c59a-4cf3-bb02-29108df457f0.png)</MultiModal>

<Checkpoint>[两个单体间形成4根分子间氢键，选项F错误](1)</Checkpoint>